JP6018294B2 - Hair care composition comprising a metathesized unsaturated polyol ester - Google Patents

Description

  The present invention relates to a hair care composition containing a gel matrix and an oligomer obtained from metathesis of unsaturated polyol esters, and a method of using the same.

  Human hair becomes dirty due to contact with the surrounding environment and sebum secreted from the scalp. When the hair becomes dirty, it becomes filthy and unappealing.

  Shampoo cleanses hair by removing excess dirt and sebum. However, shampoos can leave the hair wet, tangled and generally unwieldy. Once the hair is dry, the natural oils in the hair are removed, so the hair often becomes dry, rough, dull or curly.

  Various attempts have been made to alleviate these post-shampoo problems. One attempt is to apply a conditioner after shampooing.

  A wide variety of conditioning actives have been proposed to provide a hair conditioning effect after shampooing. These conditioning agents are known to enhance hair shine and impart moisture, softness, and static control to the hair. However, such ingredients may give a sticky, greasy or waxy feel, especially when the hair is dry.

  Silicone conditioning agents are also known to provide conditioning effects such as smoothness and good combing due to the low surface tension of silicone compounds. However, silicone conditioning agents can also cause the hair to have a dry feel or a crimped state, especially when the hair is dry. Furthermore, the increased cost and the petroleum-based nature of silicones have minimized the desirability of silicones as conditioning actives.

  Based on the above, a conditioning activity that can provide a conditioning effect to the hair and that can be used in place of or in combination with silicone or other conditioning actives to maximize the conditioning activity of the hair care composition Substances are needed. Furthermore, it is desired to find a conditioning active substance that can be obtained from natural resources, thereby providing a conditioning active substance that can be obtained from renewable resources. It would also be desirable to find a conditioning active that would yield a stable product derived from natural resources and containing a micellar surfactant system.

The invention comprises (a) from about 0.05% to about 15% by weight of the hair care composition of one or more metathesically unsaturated polyol ester oligomers ; and (b) (i) about 0.0% of the hair care composition. From 1% to about 20% by weight of one or more high melting point aliphatic compounds, (ii from about 0.1% to about 10% cationic surfactant system of the hair care composition, and (iii) hair care composition A gel matrix phase comprising an aqueous carrier of at least about 20% by weight of the product, and (c) 0.03% to 8% by weight of an anionic deposition polymer, wherein the anionic deposition polymer has a carboxyl group in its structure 10% by mass to 50% by mass of a vinyl monomer (A) having the following formula (1): CH ₂ ═C (R ¹ ) —CO—X— (Q—O) _r —R ² (1)
(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and Q represents a substituent. represents an alkylene group having 2 to 4 carbon atoms which may have, r is an integer of 2 to 15, X represents an oxygen atom or an NH group, the following structure - _{(Q-O) r} - R ² is a copolymer containing, as a monomer unit, a vinyl monomer (B) represented by 50 to 90% by mass represented by the following formula: A) has the formula ^{_{(2): CH 2 = C}} (R 3) -CO- (O- (CH 2) m -CO) n -OH (2)
(Wherein R ³ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4 and n represents an integer of 0 to 4), and an anionic adhesion polymer. For the purpose.

  The present invention is also directed to a method for washing hair using an effective amount of the above hair care composition.

  These and other features, aspects and advantages of the present invention will become apparent to those of ordinary skill in the art upon reading the present disclosure.

It is a graph which shows the comparison with HY-3050 and HY-3050 + adhesion polymer by measuring the unit (gram) of frictional force. It is a graph which shows the comparison with HY-3051 and HY-3051 + adhesion polymer by measuring the unit (gram) of a frictional force. FIG. 6 is a graph showing a comparison between HY-3050 and HY-3050 + attached polymer, where dry conditioning performance is evaluated by hair friction force measurement (IFM index). It is a graph which shows the comparison with HY-3051 and HY-3051 + adhesion polymer, and here, dry conditioning performance is evaluated by hair friction force measurement (IFM parameter | index).

In all embodiments of the invention, unless otherwise stated, all percentages are by weight of the total composition. All ratios are weight ratios unless otherwise stated. All ranges are inclusive and combinable. The number of significant digits does not represent a limitation on the displayed quantity, nor does it represent a limitation on the accuracy of the measured value. Unless otherwise indicated, all quantities are understood to be modified by the word “about”. Unless otherwise indicated, all measurements are understood to be performed at 25 ° C. and ambient conditions, and “ambient conditions” means conditions at about 1 atmosphere and about 50% relative humidity. All such weights associated with the listed ingredients are based on effective concentrations and do not include carriers or by-products that may be included in commercially available materials unless otherwise specified.
Further, in this specification, the term “adhesion polymer” has the same meaning as “DA” and “adhesion aid polymer”.

  The term “comprising”, as used herein, means that other steps and other components that do not affect the final result can be added. The term encompasses “consisting of” and “consisting essentially of”. The compositions and methods / processes of the present invention provide essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, steps, or restrictions described herein. Including, consisting of, and consisting essentially of.

  The terms “include”, “includes”, and “including”, as used herein, are meant to be non-limiting and are understood to mean “comprise”, “comprises”, and “comprising”, respectively. Is done.

  To determine the value of each of the parameters of Applicants' invention, the test method disclosed in the Test Method section of this application should be used.

  Unless stated otherwise, all concentrations of an ingredient or composition are with respect to the active portion of the ingredient or composition, and impurities that may be present in commercial sources of such ingredient or composition, such as residual solvents or By-products are excluded.

  All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated. The term “weight percent” may be denoted herein as “wt%”.

  All maximum numerical limits given throughout this specification are intended to encompass all lower numerical limits as if such lower numerical limits were expressly set forth herein. Should be understood. All minimum numerical limits described throughout this specification include all higher numerical limits as if such higher numerical limits were expressly set forth herein. All numerical ranges described throughout this specification are all narrower within such wider numerical ranges as if such narrower numerical ranges were expressly set forth herein. Includes numerical range.

A. The metathesized oligomer hair care composition comprises from about 0.05% to about 15%, alternatively from about 0.1% to about 10%, alternatively from about 0.25% to about 5% by weight of the hair care composition. One or more oligomers derived from the metathesis of unsaturated polyol esters. Exemplary metathesis unsaturated polyol esters and their starting materials are described in US Patent Application No. 2009/0220443 A1, which is incorporated herein by reference.

  A metathesized unsaturated polyol ester refers to the product obtained when one or more unsaturated polyol ester components undergo a metathesis reaction. Metathesis is a catalytic reaction involving the exchange of alkylidene units in a compound containing one or more double bonds by formation and cleavage of carbon-carbon double bonds (ie, olefinic compounds). Metathesis can occur between two identical molecules (often referred to as self-metathesis) and / or can occur between two different molecules (often referred to as cross-metathesis). Self-metathesis can be schematically represented as shown in Equation I:

式中、Ｒ¹及び²は、有機基である。

In the formula, R ¹ and ² are organic groups.

  Cross metathesis can be represented schematically as shown in Equation II:

式中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、有機基である。

In the formula, R ¹ , R ² , R ³ , and R ⁴ are organic groups.

  If the unsaturated polyol ester contains molecules with more than one carbon-carbon double bond (ie, polyunsaturated polyol ester), self-metathesis results in oligomerization of the unsaturated polyol ester. Self-metathesis reactions result in the formation of metathesis dimers, metathesis trimers, metathesis tetramers. Higher order metathesis oligomers, such as metathesis spectamers and metathesis hexamers, can also be formed by continued self-metathesis, the number and type of chains connecting unsaturated polyol ester materials, and the number of esters and esters with respect to unsaturation Depends on the orientation.

  As a starting material, a metathesized unsaturated polyol ester is prepared from one or more unsaturated polyol esters. As used herein, the term “unsaturated polyol ester” refers to a compound having two or more hydroxyl groups, wherein at least one of the hydroxyl groups is in the form of an ester, It has an organic group containing at least one carbon-carbon double bond. In many embodiments, the unsaturated polyol ester can be represented by the general structure I:

式中、ｎ≧１であり、ｍ≧０であり、ｐ≧０であり、（ｎ＋ｍ＋ｐ）≧２であり、Ｒは、有機基であり、Ｒ’は、少なくとも１つの炭素−炭素二重結合を有する有機基であり、Ｒ”は、飽和有機基である。不飽和ポリオールエステルの代表的な実施形態は、米国特許出願公開第２００９／０２２０４４３ Ａ１号に詳述されている。

In which n ≧ 1, m ≧ 0, p ≧ 0, (n + m + p) ≧ 2, R is an organic group, and R ′ is at least one carbon-carbon double bond. R ″ is a saturated organic group. Representative embodiments of unsaturated polyol esters are described in detail in US Patent Application Publication No. 2009/0220443 A1.

  In many embodiments of the invention, the unsaturated polyol ester is an unsaturated ester of glycerol. Sources of unsaturated polyol esters of glycerol include synthetic oils, natural oils (eg, vegetable oils, algal oils, bacterial derived oils, and animal fats), combinations thereof, and the like. Regenerated used vegetable oil can also be used. Representative examples of vegetable oils include argan oil, canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, high oleo oil soybean oil High oleoyl sunflower oil, linseed oil, palm kernel oil, kiri oil, castor oil, high elca rapeseed oil, jatropha oil, combinations thereof, and the like. Typical examples of animal fats include lard, tallow, chicken fat, yellow fat, fish oil, and combinations thereof. A typical example of synthetic oil is tall oil, which is a by-product of wood pulp production.

Other examples of unsaturated polyol esters include diesters such as those derived from ethylene glycol or propylene glycol, esters such as those derived from pentaerythritol or dipentaerythritol, or sugar esters such as SEFOSE® Is mentioned. Sugar esters such as SEFOSE® include one or more types of sucrose polyesters, and up to 8 ester groups can undergo a metathesis exchange reaction. Since sucrose polyester is derived from natural sources, the use of sucrose polyester can have a positive impact on the environment. Sucrose polyester is a polyester material that has multiple substitution positions around the sucrose backbone in addition to fatty chain length, saturation, and derived variables. Such sucrose polyesters can have an esterification (“IBAR”) greater than about 5. In one embodiment, the sucrose polyester may have an IBAR of about 5 to about 8. In another embodiment, the sucrose polyester has an IBAR of about 5-7, and in another embodiment, the sucrose polyester has an IBAR of about 6. In yet another embodiment, the sucrose polyester has an IBAR of about 8. Since sucrose polyester is derived from natural sources, there may be a distribution within the IBAR and chain length. For example, a sucrose polyester having 6 IBARs is mostly about 6 IBARs and may contain a mixture of some about 5 IBARs and some about 7 IBARs. Further, such sucrose polyesters may have saturation, i.e., an iodine number ("IV") of about 3 to about 140. In another embodiment, the sucrose polyester may have an IV of about 10 to about 120. In yet another embodiment, the sucrose polyester can have an IV of about 20 to about 100. Further, such sucrose polyesters have a chain length of about C _{12 to} C ₂₀ but are not limited to these chain lengths.

  Non-limiting examples of sucrose polyesters suitable for use include SEFOSE (R) 1618S, SEFOSE (R) 1618U, SEFOSE (R) 1618H, Sefa Soyate IMF 40, Sefa Soyate LP426, SEFOSE (R) Trademark) 2275, SEFOSE (registered trademark) C1695, SEFOSE (registered trademark) C18: 095, SEFOSE (registered trademark) C1495, SEFOSE (registered trademark) 1618H B6, SEFOSE (registered trademark) 1618S B6, SEFOSE (registered trademark) 1618U B6, Sefa Cotton, SEFOSE (registered trademark) C1295, Sefa C895, Sefa C1095, SEFOSE (registered trademark) 1618S B4.5 That is, Co. All of these are The Procter and Gamble (Cincinnati, Ohio).

  Other examples of suitable natural polyol esters include, but are not limited to, sorbitol esters, maltitol esters, sorbitan esters, maltodextrin-derived esters, xylitol esters, and other sugar-derived esters.

  In other embodiments, the ester ester chain length is not limited to C8-C22 or even chain length, and polyol ester feedstocks that may have even and odd chains and short and long chains for self-metathesis reactions. Natural esters by cometathesis of the resulting fats and short chain olefins (both natural and synthetic) can be included. Suitable short chain olefins include ethylene and butene.

  Oligomers obtained from metathesis of unsaturated polyol esters may be further modified by hydrogenation. For example, in certain embodiments, oligomers may be hydrogenated about 60% or more, in certain embodiments, about 70% or more, and in certain embodiments, about 80% or more hydrogenated. In certain embodiments, about 85% or more may be hydrogenated, in certain embodiments, about 90% or more may be hydrogenated, and in certain embodiments, approximately 100% may be hydrogenated.

In some embodiments, the triglyceride oligomer is obtained from the self-metathesis of soybean oil. Soy oligomers can include hydrogenated soy polyglycerides. Moreover, soy oligomer may comprise a C ₁₅ -C ₂₃ alkane as a by-product. An example of a metathesis-derived soy oligomer is fully hydrogenated DOW CORNING® HY-3050 soy wax, available from Dow Corning.

  In other embodiments, the metathesis unsaturated polyol ester can be used as a blend with one or more non-metathesis unsaturated polyol esters. The non-metathesized unsaturated polyol ester may be fully or partially hydrogenated. An example of this is DOW CORNING® HY-3051, which is a blend of HY-3050 oligomer and hydrogenated soybean oil (HSBO), available from Dow Corning. In some embodiments of the present invention, the non-metathesized unsaturated polyol ester is an unsaturated ester of glycerol. Sources of unsaturated polyol esters of glycerol include synthetic oils, natural oils (eg, vegetable oils, algal oils, bacterial oils, and animal fats), combinations thereof, and the like. Regenerated vegetable oil may be used. Illustrative examples of vegetable oils include those listed above.

  Another modification of the polyol ester oligomer may be partial amidation of a fraction of the ester with ammonia or higher organic amines such as dodecylamine or other aliphatic amines. This modification changes the overall oligomer composition, but may be useful in some applications that increase the lubricity of the product. Another modification may be by partial amidation of polyamines that may impart some pseudocationicity to the polyol ester oligomer. Such an example is DOW CORNING® material HY-3200. Other exemplary embodiments of amide functionalized oligomers are described in detail in WO2012006324 A1, which is hereby incorporated by reference.

  Polyol ester oligomers may be further modified by partial hydroformylation of unsaturated functional groups to provide one or more OH groups and increase the hydrophilicity of the oligomer.

  In certain embodiments, the metathesized unsaturated polyol ester and blend are formulated as a small particle emulsion. Triglyceride oligomer emulsions can be prepared with one or more surfactants selected from nonionic, zwitterionic, cationic, and anionic surfactants. In another embodiment, the metathesized unsaturated polyol ester is pre-melted prior to emulsification and formulated into the hair care composition.

  In other embodiments, unsaturated polyol esters and blends may be modified prior to oligomerization to incorporate near-end branching. Exemplary polyol esters that are modified prior to oligomerization to incorporate terminal branching are described in WO 2012/009525 A2, which is hereby incorporated by reference.

B. Cationic Surfactant System The composition of the present invention comprises a cationic surfactant system. The cationic surfactant system may be a single cationic surfactant or a mixture of two or more cationic surfactants. Preferably, the cationic surfactant system comprises a mono long chain alkyl quaternized ammonium salt; a combination of mono long chain alkyl quaternized ammonium salt and di long chain alkyl quaternized ammonium salt; mono long chain alkyl amide amine salt A combination of a mono long chain alkylamidoamine salt and a dilong chain alkyl quaternized ammonium salt; a combination of a mono long chain alkylamidoamine salt and a mono long chain alkyl quaternized ammonium salt;

  The cationic surfactant is from about 0.1% to about 10%, preferably from about 0.5% to about 8%, more preferably from about 0.8% to about 5%, and even more. Preferably it is included in the composition at a concentration of about 1.0% to about 4% by weight.

Mono Long Chain Alkyl Quaternized Ammonium Salts Monoalkyl quaternized ammonium salt cationic surfactants useful herein are 12-30 carbon atoms, preferably 16-24 carbon atoms, more preferably It has one long alkyl chain with a C18-22 alkyl group. The remaining groups bonded to nitrogen are independently alkyl groups having 1 to about 4 carbon atoms, or alkoxy groups, polyoxyalkylene groups, alkylamide groups, hydroxyalkyls having up to about 4 carbon atoms. Selected from a group, an aryl group, or an alkylaryl group.

  Mono long chain alkyl quaternized ammonium salts useful herein are those having the following formula (I):

式中、Ｒ⁷⁵、^R76、Ｒ⁷⁷、及びＲ⁷⁸のうちの１つは、炭素原子数１２〜３０のアルキル基、又は炭素原子数が最大約３０個の芳香族基、アルコキシ基、ポリオキシアルキレン基、アルキルアミド基、ヒドロキシアルキル基、アリール基、若しくはアルキルアリール基から選択され、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸の残りは、独立して、炭素原子数１〜約４のアルキル基、又は炭素原子数が最大約４個のアルコキシ基、ポリオキシアルキレン基、アルキルアミド基、ヒドロキシアルキル基、アリール基、若しくはアルキルアリール基から選択され、Ｘ^-は、塩形成アニオン、例えば、ハロゲン（例えば、塩化物、臭化物）ラジカル、酢酸ラジカル、クエン酸ラジカル、乳酸ラジカル、グリコール酸ラジカル、リン酸ラジカル、硝酸ラジカル、スルホン酸ラジカル、硫酸ラジカル、アルキル硫酸ラジカル、及びアルキルスルホン酸ラジカルから選択されるものである。アルキル基は、炭素原子及び水素原子に加えて、エーテル結合及び／又はエステル結合、並びにアミノ基等の他の基を含有してよい。より長鎖のアルキル基、例えば、炭素原子数約１２以上のものは、飽和であっても不飽和であってもよい。好ましくは、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸のうちの１つは、炭素原子数１２〜３０、より好ましくは炭素原子数１６〜２４、更により好ましくは炭素原子数１８〜２２、なお更に好ましくは炭素原子数２２のアルキル基から選択され、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸の残りは、独立して、ＣＨ₃、Ｃ₂Ｈ₅、Ｃ₂Ｈ₄ＯＨ、及びこれらの混合物から選択され、Ｘは、Ｃｌ、Ｂｒ、ＣＨ₃ＯＳＯ₃、Ｃ₂Ｈ₅ＯＳＯ₃、及びこれらの混合物からなる群から選択される。

Wherein one of R ⁷⁵ , ^{R 76} , R ⁷⁷ , and R ⁷⁸ is an alkyl group having 12 to 30 carbon atoms, or an aromatic group, alkoxy group, polyoxy having up to about 30 carbon atoms Selected from an alkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group, or an alkylaryl group, the remainder of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are independently from 1 to about 4 carbon atoms An alkyl group, or an alkoxy group having up to about 4 carbon atoms, a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group, or an alkylaryl group, wherein X ⁻ is a salt-forming anion, for example, Halogen (eg, chloride, bromide) radicals, acetic acid radicals, citric acid radicals, lactic acid radicals, glycolic acid radicals, phosphoric acid radicals, nitric acid radicals, Acid radicals, is selected from sulfuric acid radicals, alkyl sulfate radicals, and alkyl sulfonate radicals. The alkyl group may contain other groups such as ether bonds and / or ester bonds, and amino groups in addition to carbon atoms and hydrogen atoms. Longer chain alkyl groups, such as those having about 12 or more carbon atoms, may be saturated or unsaturated. Preferably, one of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ has 12 to 30 carbon atoms, more preferably 16 to 24 carbon atoms, still more preferably 18 to 22 carbon atoms, Even more preferably selected from alkyl groups of 22 carbon atoms, the remainder of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently CH ₃ , C ₂ H ₅ , C ₂ H ₄ OH, and Selected from these mixtures, X is selected from the group consisting of Cl, Br, CH ₃ OSO ₃ , C ₂ H ₅ OSO ₃ , and mixtures thereof.

  Non-limiting examples of such mono long chain alkyl quaternized ammonium salt cationic surfactants include behenyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, cetyl trimethyl ammonium salt, and hydrogenated tallow alkyl trimethyl ammonium salt. Can be mentioned.

Mono long chain alkylamidoamine salts Mono long chain alkylamines are also suitable as cationic surfactants. Primary, secondary and tertiary aliphatic amines are useful. Particularly useful are tertiary amidoamines having alkyl groups of about 12 to about 22 carbons. Typical tertiary amidoamines include stearamidepropyldimethylamine, stearamidepropyldiethylamine, stearamideethyldiethylamine, stearamideethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, Palmitamidoethyldimethylamine, behenamidepropyldimethylamine, behenamidepropyldiethylamine, behenamideethyldiethylamine, behenamideethyldimethylamine, arachimidamidepropyldimethylamine, arachimidamidepropyldiethylamine, arachimidamideethyldiethylamine, arachi Examples thereof include damidoethyldimethylamine and diethylaminoethyl stearamide. Amines useful in the present invention are disclosed in US Pat. No. 4,275,055 (Nachtigal et al.). These amines include L-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L-glutamic acid hydrochloride, maleic acid, and mixtures thereof, more preferably L-glutamic acid, It can be used in combination with an acid such as lactic acid or citric acid. The amines herein may be partially from any acid with a molar ratio of amine to acid of about 1: 0.3 to about 1: 2, more preferably about 1: 0.4 to about 1: 1. It is preferable to neutralize.

Di-long-chain alkyl quaternized ammonium salt The di-long-chain alkyl quaternized ammonium salt is preferably combined with a mono-long-chain alkyl quaternized ammonium salt or a mono-long-chain alkylamidoamine salt. Such a combination is believed to be able to provide an easy rinsing sensation as compared to the single use of monoalkyl quaternized ammonium salts or mono long chain alkylamidoamine salts alone. In such a combination with a mono long chain alkyl quaternized ammonium salt or a mono long chain alkyl amide amine salt, the di long chain alkyl quaternized ammonium salt is a dialkyl quaternized ammonium salt in a cationic surfactant system. It is used at a concentration such that the weight percent ranges preferably from about 10% to about 50%, more preferably from about 30% to about 45%.

  Dialkyl quaternized ammonium salt cationic surfactants useful herein are 2 to 30 carbon atoms, preferably 16 to 24 carbon atoms, more preferably 18 to 22 carbon atoms. Having two long alkyl chains. The remaining groups bonded to nitrogen are independently alkyl groups having 1 to about 4 carbon atoms, or alkoxy groups, polyoxyalkylene groups, alkylamide groups, hydroxyalkyls having up to about 4 carbon atoms. Selected from a group, an aryl group, or an alkylaryl group.

  Dilong chain alkyl quaternized ammonium salts useful herein are those having the following formula (II):

式中、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸のうちの２つは、炭素原子数１２〜３０のアルキル基、又は炭素原子数が最大約３０個の、芳香族基、アルコキシ基、ポリオキシアルキレン基、アルキルアミド基、ヒドロキシアルキル基、アリール基、若しくはアルキルアリール基から選択され、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸の残りは、独立して、炭素原子数１〜約４のアルキル基、又は炭素原子数が最大約４個の、アルコキシ基、ポリオキシアルキレン基、アルキルアミド基、ヒドロキシアルキル基、アリール基、若しくはアルキルアリール基から選択され、Ｘ^-は、塩形成アニオン、例えば、ハロゲン（例えば、塩化物、臭化物）ラジカル、酢酸ラジカル、クエン酸ラジカル、乳酸ラジカル、グリコール酸ラジカル、リン酸ラジカル、硝酸ラジカル、スルホン酸ラジカル、硫酸ラジカル、アルキル硫酸ラジカル、及びアルキルスルホン酸ラジカルから選択されるものである。アルキル基は、炭素原子及び水素原子に加えて、エーテル結合及び／又はエステル結合、並びにアミノ基等の他の基を含有してよい。より長鎖のアルキル基、例えば、炭素原子数約１２以上のものは、飽和であっても不飽和であってもよい。好ましくは、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸のうちの１つは、炭素原子数１２〜３０、より好ましくは炭素原子数１６〜２４、更により好ましくは炭素原子数１８〜２２、なお更に好ましくは炭素原子数２２のアルキル基から選択され、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸の残りは、独立して、ＣＨ₃、Ｃ₂Ｈ₅、Ｃ₂Ｈ₄ＯＨ、及びこれらの混合物から選択され、Ｘは、Ｃｌ、Ｂｒ、ＣＨ₃ＯＳＯ₃、Ｃ₂Ｈ₅ＯＳＯ₃、及びこれらの混合物からなる群から選択される。

In the formula, two of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are alkyl groups having 12 to 30 carbon atoms, or aromatic groups, alkoxy groups having up to about 30 carbon atoms, Selected from a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group, or an alkylaryl group, the remainder of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are independently from 1 to about Selected from an alkyl group of 4 or an alkoxy group, polyoxyalkylene group, alkylamide group, hydroxyalkyl group, aryl group or alkylaryl group having up to about 4 carbon atoms, wherein X ⁻ is a salt-forming anion , For example, halogen (eg, chloride, bromide) radicals, acetic acid radicals, citric acid radicals, lactic acid radicals, glycolic acid radicals, phosphoric acid radicals, radical nitrates , Sulfonic acid radicals, is selected from sulfuric acid radicals, alkyl sulfate radicals, and alkyl sulfonate radicals. The alkyl group may contain other groups such as ether bonds and / or ester bonds, and amino groups in addition to carbon atoms and hydrogen atoms. Longer chain alkyl groups, such as those having about 12 or more carbon atoms, may be saturated or unsaturated. Preferably, one of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ has 12 to 30 carbon atoms, more preferably 16 to 24 carbon atoms, still more preferably 18 to 22 carbon atoms, Even more preferably selected from alkyl groups of 22 carbon atoms, the remainder of R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently CH ₃ , C ₂ H ₅ , C ₂ H ₄ OH, and Selected from these mixtures, X is selected from the group consisting of Cl, Br, CH ₃ OSO ₃ , C ₂ H ₅ OSO ₃ , and mixtures thereof.

  Such dialkyl quaternized ammonium salt cationic surfactants include, for example, dialkyl (14-18) dimethylammonium chloride, ditallowalkyldimethylammonium chloride, dihydro-added tallowalkyldimethylammonium chloride, distearyldimethylammonium chloride, And dicetyldimethylammonium chloride. Examples of such dialkyl quaternized ammonium salt cationic surfactants include asymmetric dialkyl quaternized ammonium salt cationic surfactants.

C. High melting point aliphatic compounds High melting point aliphatic compounds useful herein are those selected from the group consisting of aliphatic alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof having a melting point of 25 ° C or higher. Is done. One skilled in the art will recognize that the compounds disclosed in this section of the specification may belong to more than one class in some cases (eg, some fatty alcohol derivatives may also be classified as fatty acid derivatives). ) However, a given classification is not intended to limit that particular compound, but is done as such for convenience of classification and nomenclature. Furthermore, those skilled in the art have also found that depending on the number and position of double bonds and the length and position of branches, the melting point of certain compounds having certain essential carbon atoms can be less than 25 ° C. Such low melting point compounds are not included in this section. Non-limiting examples of high melting point compounds are described in International Cosmetic Ingredient Dictionary (Fifth Edition, 1993) and CTFA Cosmetic Ingredient Handbook (Second Edition, 1992).

  Of the various high melting point aliphatic compounds, aliphatic alcohols are preferably used in the compositions of the present invention. The fatty alcohols useful herein are those having from about 14 to about 30 carbon atoms, preferably from about 16 to about 22 carbon atoms. These aliphatic alcohols are saturated and may be straight chain alcohols or branched chain alcohols. Preferred aliphatic alcohols include, for example, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.

  High melting point aliphatic compounds from single compounds of high purity are preferred. Highly preferred is a single compound from a pure aliphatic alcohol selected from the group of pure cetyl alcohol, stearyl alcohol and behenyl alcohol. As used herein, “pure” means that the compound has a purity of at least about 90%, preferably at least about 95%. These high purity single compounds provide good rinsability from the hair when the consumer rinses the composition.

  Considering that high melting point aliphatic compounds provide improved conditioning benefits, such as a smooth feel while applied to wet hair, softness and moist feel in dry hair, about 0% of the composition. 0.1% to about 20% by weight, preferably about 1% to about 15% by weight, more preferably about 1.5% to about 8% by weight in the composition.

D. Aqueous carrier The gel matrix of the hair care composition of the present invention comprises an aqueous carrier. Thus, the formulations of the present invention may be in the form of a liquid that can be poured (under ambient conditions). Accordingly, such compositions typically comprise an aqueous carrier, which is present at a concentration of about 20% to about 95%, or even about 60% to about 85% by weight. An aqueous carrier can include water or a compatible mixture of water and an organic solvent, but in one aspect, is minimal unless it is accidentally incorporated into the composition as a minor component of another component. Or it may contain water with a very low concentration of organic solvent.

  Aqueous carriers useful in the present invention include water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. Lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, and in one embodiment ethanol and isopropanol. Polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propanediol.

  According to embodiments of the present invention, the hair care composition may have a pH in the range of about 2 to about 10 at 25 ° C. In one embodiment, the hair care composition has a pH in the range of about 2 to about 6, which can help solubilize minerals and redox metals already attached to the hair. Thus, the hair care composition may also be effective in washing away existing minerals and redox metal deposits, thereby reducing cuticle deformation and reducing cuticle chipping and damage. it can.

E. Gel Matrix The composition of the present invention comprises a gel matrix. The gel matrix includes a cationic surfactant, a high melting point aliphatic compound, and an aqueous carrier.

  Gel matrices are suitable for providing a variety of conditioning effects, such as a slick feel during application to wet hair, as well as a soft and moist feel in dry hair. In view of providing the gel matrix, the cationic surfactant and the high melting point aliphatic compound preferably have a weight ratio of the cationic surfactant to the high melting point aliphatic compound of about 1: 1 to about 1: 10 and more preferably in a concentration ranging from about 1: 1 to about 1: 6.

F. Further constituents Silicone Conditioning Agent According to an embodiment of the present invention, the hair care composition comprises a silicone conditioning agent comprising a silicone compound. The silicone compound may include volatile silicone, non-volatile silicone, or a combination thereof. In one embodiment, non-volatile silicone is used. When volatile silicones are present, they are typically associated with their use as solvents or carriers for commercially available forms of non-volatile silicone material components such as silicone rubbers and resins. The silicone compound may include a silicone fluid conditioning agent and may include other components such as silicone resins to improve the deposition efficiency of the silicone fluid or enhance hair gloss. The concentration of the silicone compound in the conditioner composition is typically, for example, from about 0.01 wt% to about 10 wt%, from about 0.1 wt% to about 8 wt%, from about 0.1 wt% to about It ranges from 5% by weight, or even from about 0.2% to about 3% by weight.

Exemplary silicone compounds are (a) non-volatile, does not contain an amino group substantially, first having a viscosity of about 100,000 mm ² s ^-1 ~ about 30,000,000mm ² s ^-1 (B) a second polysiloxane that is non-volatile, substantially free of amino groups, and having a viscosity of from about 5 mm ² s ⁻¹ to about 10,000 mm ² s ⁻¹ , (c) amino An aminosilicone having less than about 0.5% by weight nitrogen of the silicone, (d) a silicone copolymer emulsion having an internal phase viscosity greater than about 100 × 10 ⁶ mm ² s ⁻¹ when measured at 25 ° C., (e) Examples include silicone polymers containing quaternary groups, or (f) grafted silicone polyols. Silicone compounds (a) to (f) are disclosed in U.S. Patent Application Publication Nos. 2008/0292574, 20th. 07/0041929, 2008/0292575, and 2007/0286837, each of which is hereby incorporated by reference in its entirety.

a. First Polysiloxane The hair care composition of the present invention may comprise a first polysiloxane. The first polysiloxane is non-volatile and substantially free of amino groups. In the present invention, the first polysiloxane being “substantially free of amino groups” means that the first polysiloxane contains 0% by weight of amino groups. The first polysiloxane having a viscosity of about 100,000 mm ² s ^-1 ~ about 30,000,000mm ² s ^-1 at 25 ° C.. For example, the viscosity may range from about 300,000 mm ² s ⁻¹ to about 25,000,000 mm ² s ⁻¹ or about 10,000,000 mm ² s ⁻¹ to about 20,000,000 mm ² s ⁻¹ It's okay. The first polysiloxane has a molecular weight of about 100,000 to about 1,000,000. For example, the molecular weight may range from about 130,000 to about 800,000, or from about 230,000 to about 600,000. According to one aspect, the first polysiloxane may be nonionic.

  Exemplary first non-volatile polysiloxanes useful herein include those according to the following general formula (I):

式中、Ｒは、アルキル又はアリールであり、ｐは、約１，３００〜約１５，０００、例えば、約１，７００〜約１１，０００、又は約３，０００〜約８，０００の整数である。Ｚは、シリコーン鎖の末端をブロックする基を表す。シロキサン鎖において置換されるアルキル若しくはアリール基（Ｒ）又はシロキサン鎖の末端において置換されるアルキル若しくはアリール基Ｚは、得られるシリコーンが室温で流体のままであり、分散性があり、毛髪に塗布されたときに刺激性がなく、毒性やその他の害もなく、組成物の他の構成成分と相溶性であり、通常の使用及び保管条件下で化学的に安定であり、毛髪に付着することができ、毛髪の状態を整える限り、任意の構造を有してよい。ある実施形態によれば、好適なＺ基としては、ヒドロキシ、メチル、メトキシ、エトキシ、プロポキシ、及びアリールオキシが挙げられる。各ケイ素原子における２つのＲ基は、同じ基を表しても異なる基を表してもよい。１つの実施形態によれば、２つのＲ基は、同じ基を表し得る。好適なＲ基としては、メチル、エチル、プロピル、フェニル、メチルフェニル及びフェニルメチルが挙げられる。例示的なシリコーン化合物としては、ポリジメチルシロキサン、ポリジエチルシロキサン及びポリメチルフェニルシロキサンが挙げられる。１つの実施形態によれば、ポリジメチルシロキサンが、第１のポリシロキサンである。本明細書で有用な市販のシリコーン化合物としては、例えば、Ｇｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ ＣｏｍｐａｎｙからＴＳＦ４５１シリーズで入手可能なもの、及びＤｏｗ ＣｏｒｎｉｎｇからＳＨ２００シリーズで入手可能なものが挙げられる。

Wherein R is alkyl or aryl and p is an integer from about 1,300 to about 15,000, such as from about 1,700 to about 11,000, or from about 3,000 to about 8,000. is there. Z represents a group that blocks the terminal of the silicone chain. The alkyl or aryl group (R) substituted in the siloxane chain or the alkyl or aryl group Z substituted at the end of the siloxane chain is such that the resulting silicone remains fluid at room temperature and is dispersible and applied to the hair. It is not irritating, has no toxicity or other harm, is compatible with other components of the composition, is chemically stable under normal use and storage conditions, and can adhere to hair As long as the hair condition is adjusted, it may have any structure. According to certain embodiments, suitable Z groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on each silicon atom may represent the same group or different groups. According to one embodiment, the two R groups may represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Exemplary silicone compounds include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. According to one embodiment, the polydimethylsiloxane is the first polysiloxane. Commercially available silicone compounds useful herein include, for example, those available in the TSF451 series from General Electric Company and those available in the SH200 series from Dow Corning.

Silicone compounds that can be used herein also include silicone gums. The term “silicone gum” as used herein means a polyorganosiloxane material having a viscosity of at least 1,000,000 mm ² s ⁻¹ at 25 ° C. It is recognized that the silicone gums described herein may have portions that overlap in part with the silicone compounds disclosed above. This overlap is not intended to limit any of these materials. “Silicone gums” typically have a mass molecular weight greater than about 165,000, generally from about 165,000 to about 1,000,000. Specific examples include polydimethylsiloxane, poly (dimethylsiloxane methylvinylsiloxane) copolymer, poly (dimethylsiloxane diphenylsiloxane methylvinylsiloxane) copolymer and mixtures thereof. Commercially available silicone gums useful herein include, for example, TSE200A available from General Electric Company.

b. Second Polysiloxane The hair care composition of the present invention may comprise a second polysiloxane. The second polysiloxane is non-volatile and substantially free of amino groups. In the present invention, the second polysiloxane being “substantially free of amino groups” means that the second polysiloxane contains 0% by weight of amino groups. The second polysiloxane is about 5 mm ² s ^-1 ~ about 10,000 mm ² s ^-1 at 25 ° C., for example, about 5 mm ² s ^-1 ~ about 5,000 mm ² s ^-1, about 10 mm ² s ^-1 Having a viscosity of about 1,000 mm ² s ⁻¹ , or about 20 mm ² s ⁻¹ to about 350 mm ² s ⁻¹ . The second polysiloxane has a molecular weight of about 400 to about 65,000. For example, the molecular weight of the second polysiloxane can range from about 800 to about 50,000, from about 400 to about 30,000, or from about 400 to about 15,000. According to one aspect, the second polysiloxane may be nonionic. According to another aspect, the second polysiloxane may be a linear silicone.

  Exemplary second non-volatile polysiloxanes useful herein include polyalkyl or polyaryl siloxanes according to the following general formula (II):

式中、Ｒ¹は、アルキル又はアリールであり、ｒは、約７〜約８５０、例えば、約７〜約６６５、約７〜約４００、又は約７〜約２００の整数である。Ｚ¹は、シリコーン鎖の末端をブロックする基を表す。シロキサン鎖において置換されるアルキル若しくはアリール基（Ｒ¹）又はシロキサン鎖の末端において置換されるアルキル若しくはアリール基Ｚ¹は、得られるシリコーンが室温で流体のままであり、分散性であり、毛髪に塗布されたときに刺激性がなく、毒性やその他の害もなく、組成物の他の構成成分と相溶性であり、通常の使用及び保管条件下で化学的に安定しており、毛髪に付着することができ、毛髪の状態を整える限り、任意の構造を有してよい。ある実施形態によれば、好適なＺ¹基としては、ヒドロキシ、メチル、メトキシ、エトキシ、プロポキシ、及びアリールオキシが挙げられる。各ケイ素原子における２つのＲ¹基は、同じ基をあらわしてもよいし、又は異なる基を表してもよい。１つの実施形態によれば、２つのＲ¹基は、同じ基を表し得る。好適なＲ¹基としては、メチル、エチル、プロピル、フェニル、メチルフェニル及びフェニルメチルが挙げられる。例示的なシリコーン化合物としては、ポリジメチルシロキサン、ポリジエチルシロキサン、及びポリメチルフェニルシロキサンが挙げられる。１つの実施形態によれば、ポリジメチルシロキサンは、第２のポリシロキサンである。本明細書で有用な市販のシリコーン化合物としては、例えば、Ｇｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ ＣｏｍｐａｎｙからＴＳＦ４５１シリーズで入手可能なもの、及びＤｏｗ ＣｏｒｎｉｎｇからＳＨ２００シリーズで入手可能なものが挙げられる。

Wherein R ¹ is alkyl or aryl and r is an integer from about 7 to about 850, such as from about 7 to about 665, from about 7 to about 400, or from about 7 to about 200. Z ¹ represents a group that blocks the terminal of the silicone chain. The alkyl or aryl group (R ¹ ) substituted in the siloxane chain or the alkyl or aryl group Z ¹ substituted at the end of the siloxane chain is such that the resulting silicone remains fluid at room temperature, is dispersible, When applied, it is not irritating, has no toxicity or other harm, is compatible with the other components of the composition, is chemically stable under normal use and storage conditions, and adheres to the hair It can have any structure as long as the hair condition is adjusted. According to certain embodiments, suitable Z ¹ groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R ¹ groups on each silicon atom may represent the same group or may represent different groups. According to one embodiment, the two R ¹ groups may represent the same group. Suitable R ¹ groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Exemplary silicone compounds include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. According to one embodiment, the polydimethylsiloxane is a second polysiloxane. Commercially available silicone compounds useful herein include, for example, those available in the TSF451 series from General Electric Company and those available in the SH200 series from Dow Corning.

c. Aminosilicone The hair care composition of the present invention contains less than about 0.5%, such as less than about 0.2%, or less than about 0.1% by weight of nitrogen of the aminosilicone in view of the friction reducing effect. It may contain amino silicone. Surprisingly, it has been found that higher concentrations of nitrogen (amine functional groups) in the aminosilicone tend to reduce friction reduction, resulting in lower conditioning effects obtained from aminosilicone. The aminosilicones useful herein can have at least one silicone block with more than 200 siloxane units, taking into account the friction reducing effect. Aminosilicones useful herein include, for example, quaternized aminosilicones and non-quaternized aminosilicones.

  In one embodiment, the aminosilicones useful herein are water insoluble. In the present invention, “water-insoluble aminosilicone” is 10 g or less per 100 g of water at 25 ° C., in another embodiment, 5 g or less per 100 g of water at 25 ° C., and in another embodiment 1 g per 100 g of water at 25 ° C. An aminosilicone having the following solubility is meant. In the present invention, “water-insoluble aminosilicone” means that the aminosilicone is substantially free of copolyol groups. When present, the copolyol group is present at a concentration of less than 10%, less than 1%, or less than 0.1% by weight of the aminosilicone.

According to one embodiment, the aminosilicones useful herein are those that conform to general formula (III).
^{_{(R 2) a G 3-}} a -Si (-O-SiG 2) n (-O-SiG b (R 2) 2-b) m -O-SiG 3-a (R 2) a (IIII)
Wherein, G is hydrogen, phenyl, hydroxy, or C ₁ -C ₈ alkyl, such as methyl, a is an integer of 1 to 3 values, for example 1, b is 0 to 2 values An integer having, for example, 1, n is a number from 1 to 2,000, for example 100 to 1,800, 300 to 800, or 500 to 600, and m has a value from 0 to 1,999. An integer, for example 0-10 or 0, R ² is a monovalent radical corresponding to the general formula C _q H _2q L, where q is an integer having a value of 2-8, L is , the following _{^{groups: -N (R 3 2) CH}} 2 -CH 2 -N (R 3 2) 2; -N (R 3) 2; -N + (R 3) 3 a -; -N (R 3 ^{_{) CH 2 -CH 2 -N + R}} 3 H 2 A - is selected from wherein R ³ is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, for example from about C ₁ ~ Is an alkyl radical of about C ₂₀ and A ⁻ is a halide ion. According to certain embodiments, L is —N (CH ₃ ) ₂ or —NH ₂ . According to another embodiment, L is —NH ₂ .

  The aminosilicone of the above formula is about 0.1% to about 5% by weight of the composition, alternatively about 0.2% to about 2%, alternatively about 0.2% to about 1.0%, Alternatively, it is used at a concentration of about 0.3 wt% to about 0.8 wt%.

According to one embodiment, the aminosilicone is a compound corresponding to formula (III) wherein m = 0, a = 1, q = 3, G = methyl, n is from about 1400 to about 1700, for example About 1600 and L may include —N (CH ₃ ) ₂ or —NH ₂ , such as —NH ₂ . According to another embodiment, the aminosilicone is a compound corresponding to formula (III) wherein m = 0, a = 1, q = 3, G = methyl, n is about 400 to about 800, for example From about 500 to about 600, and L may include —N (CH ₃ ) ₂ or —NH ₂ , such as —NH ₂ . Thus, the aminosilicones described above may also be referred to as terminal aminosilicones because one or both ends of the silicone chain terminate with a nitrogen-containing group. Such terminal aminosilicones can provide improved friction reduction compared to grafted aminosilicones.

  Another example of an aminosilicone useful herein includes, for example, a quaternized aminosilicone having the trade name KF8020 available from Shinetsu.

When the aminosilicone described above is formulated into a hair care composition, it can be mixed with a solvent having a lower viscosity. Such solvents include, for example, polar or nonpolar volatile or non-volatile oils. Such oils include, for example, silicone oils, hydrocarbons, and esters. Among such various solvents, exemplary solvents include those selected from the group consisting of nonpolar volatile hydrocarbons, volatile cyclic silicones, non-volatile linear silicones, and mixtures thereof. Useful volatile linear silicones herein is from about 1 mm ² s ^-1 ~ about 20,000 mm ² s ^-1 at 25 ° C., for example, of about 20 mm ² s ^-1 ~ about 10,000 mm ² s ^-1 It has a viscosity. According to one embodiment, the solvent reduces the viscosity of the aminosilicone and provides improved hair conditioning benefits such as friction reduction in dry hair, especially non-polar volatile hydrocarbons, especially Nonpolar volatile isoparaffin. Such a mixture may have a viscosity of about 1,000 mPas to about 100,000 mPas, alternatively about 5,000 mPas to about 50,000 mPas.

d. Silicone Copolymer Emulsion The hair care composition of the present invention may comprise a silicone copolymer emulsion having an internal phase viscosity of greater than about 100 × 10 ⁶ mm ² s ⁻¹ . The silicone copolymer emulsion is about 0.1% to about 15%, alternatively about 0.3% to about 10%, alternatively about 0.5% by weight of the composition in view of providing a clean feel. It can be present in an amount from% to about 5% by weight.

According to one embodiment, the silicone copolymer emulsion is greater than about 100 × 10 ⁶ mm ² s ⁻¹ at 25 ° C., alternatively ^greater than about 120 × 10 ⁶ mm ² s ⁻¹ , alternatively about 150 × 10 ⁶ mm ² s. ^Has a viscosity of ^-1 . According to another embodiment, the silicone copolymer emulsion is less than about 1000 × 10 ⁶ mm ² s ⁻¹ at 25 ° C., alternatively less than about 500 × 10 ⁶ mm ² s ⁻¹ , alternatively about 300 × 10 ⁶ mm ² s ^{−1. Has} a viscosity of less than ^-1 . In order to determine the internal phase viscosity of a silicone copolymer emulsion, the polymer may first be detached from the emulsion. As an example, the following procedure can be used to cleave the polymer from the emulsion: 1) Add 10 grams of the emulsion sample to 15 milliliters of isopropyl alcohol, 2) Mix well with a spatula, 3) Isopropyl Decant the alcohol 4) Add 10 ml of acetone and knead the polymer with a spatula 5) Decant the acetone 6) Place the polymer in an aluminum container and flatten / drain with a paper towel, 7 ) Dry at 80 ° C. for 2 hours. The polymer can then be tested using any known rheometer, such as, for example, a CarriMed, Haake, or Monsanto rheometer operating in dynamic shear mode. The internal phase viscosity value can be obtained by recording the dynamic viscosity (n ′) at a frequency point of 9.900 × 10 ⁻³ Hz. According to one embodiment, the average particle size of the emulsion is less than about 1 micrometer, for example, less than about 0.7 micrometers.

  The silicone copolymer emulsion of the present invention may comprise a silicone copolymer, at least one surfactant, and water.

Silicone copolymers are produced as a result of the addition reaction of the following two materials in the presence of a metal-containing catalyst.
(I) Polysiloxane having reactive groups at both ends represented by the general formula (IV):

（式中、
Ｒ⁴は、例えば、水素原子、エチレン性不飽和を有する脂肪族基（すなわち、ビニル、アリル、又はヘキセニル）、ヒドロキシル基、アルコキシル基（すなわち、メトキシ、エトキシ、又はプロポキシ）、アセトキシル基、又はアミノ若しくはアルキルアミノ基等の鎖付加反応により反応可能な基であり、
Ｒ⁵は、アルキル、シクロアルキル、アリール、又はアルキルアリールであり、エーテル、ヒドロキシル、アミン、カルボキシル、チオール、エステル、及びスルホネート等の更なる官能基を含んでもよく、１つの実施形態では、Ｒ⁵は、メチルである。所望により、実質的に直鎖状であるが少量の分岐を有するポリマーを生成するために、低モルパーセントの基が、Ｒ⁵について上に記載したような反応性基であってもよい。この場合、Ｒ⁴基と等価なＲ⁵基の濃度は、モルパーセント基準で約１０％未満、例えば約２％未満であってよい。
ｓは、式（ＩＶ）のポリシロキサンが、約１ｍｍ²ｓ^-1〜約１×１０⁶ｍｍ²ｓ^-1の粘度を有するような値を有する整数である。）
及び、
（ｉｉ）式（ＩＶ）のポリシロキサンのＲ⁴基と反応可能な少なくとも１つ若しくは多くとも２つの基を含む、少なくとも１つのシリコーン化合物又は非シリコーン化合物。１つの実施形態によれば、反応性基は、エチレン性不飽和を有する脂肪族基である。

(Where
R ⁴ is, for example, a hydrogen atom, an aliphatic group having ethylenic unsaturation (ie, vinyl, allyl, or hexenyl), a hydroxyl group, an alkoxyl group (ie, methoxy, ethoxy, or propoxy), an acetoxyl group, or an amino group Or a group capable of reacting by a chain addition reaction such as an alkylamino group,
R ⁵ is alkyl, cycloalkyl, aryl, or alkylaryl, and may include additional functional groups such as ether, hydroxyl, amine, carboxyl, thiol, ester, and sulfonate, and in one embodiment, R ⁵ Is methyl. If desired, the low mole percent group may be a reactive group as described above for R ⁵ to produce a polymer that is substantially linear but has a small amount of branching. In this case, the concentration of R ⁵ groups equivalent to R ⁴ groups may be less than about 10%, such as less than about 2%, on a mole percent basis.
s is an integer having a value such that the polysiloxane of formula (IV) has a viscosity of from about 1 mm ² s ⁻¹ to about 1 × 10 ⁶ mm ² s ⁻¹ . )
as well as,
(Ii) at least one silicone compound or non-silicone compound comprising at least one or at most two groups capable of reacting with the R ⁴ group of the polysiloxane of formula (IV). According to one embodiment, the reactive group is an aliphatic group having ethylenic unsaturation.

  The metal-containing catalyst used in the above reaction is often unique to a particular reaction. Such catalysts are known in the art. In general, they are substances containing metals such as platinum, rhodium, tin, titanium, copper, lead.

  The mixture used to form the emulsion may also contain at least one surfactant. Examples of this surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, alkyl polysaccharides, and amphoteric surfactants. The above surfactants may be used individually or in combination.

  An exemplary method for making the silicone copolymer emulsion described herein is: 1) mixing the above material (a) with the above material (b), followed by material (b) being a metal-containing catalyst. Mixing a suitable metal-containing catalyst so that it can react with material (a) in the presence, 2) further mixing at least one surfactant and water, and 3) emulsifying the mixture; including. Methods for producing such silicone copolymer emulsions are disclosed in US Pat. No. 6,013,682, International Patent Publication No. 01/58986 A1, and European Patent Application 0874017 A2.

An example of a commercially available silicone copolymer emulsion is an emulsion of about 60-70% by weight divinyl dimethicone / dimethicone copolymer available from Dow Corning under the trade name HMW2220 with an internal phase viscosity of at least 120 × 10 ⁶ mm ² s ^−1. It is.

e. Silicone Polymer Containing Quaternary Group The hair care composition of the present invention may comprise a silicone polymer containing a quaternary group (ie, a quaternized silicone polymer). Quaternized silicone polymers provide improved conditioning benefits such as smooth feel, reduced friction, and prevention of hair damage. In particular, quaternary groups can have good affinity with damaged / dyed hair. The quaternized silicone polymer is present in an amount from about 0.1% to about 15% by weight, based on the total weight of the hair conditioning composition. For example, according to certain embodiments, the quaternized silicone polymer is about 0.2% to about 10%, alternatively about 0.3% to about 5%, alternatively about 0.5% by weight of the composition. % To about 4% by weight.

The quaternized silicone polymer of the present invention is composed of at least one silicone block and at least one non-silicone block containing a quaternary nitrogen group, the number of non-silicone blocks being one more than the number of silicone blocks. . The silicone polymer corresponds to the following general structure (V).
A ¹ -B- (A ² -B) _m -A ¹ (V)
Where B is a silicone block having more than 200 siloxane units, A ¹ is a terminal group that may contain quaternary groups, and A ² is a non-silicone block containing quaternary nitrogen groups. , M is an integer of 0 or more, provided that when m = 0, the A ¹ group contains a quaternary group.

  Structures corresponding to the above general formula are described in, for example, US Pat. No. 4,833,225, US Patent Application Publication No. 2004/0138400, US Patent Application Publication No. 2004/0048996, and US Patent Application Publication No. 2008 / No. 0925575.

  In one embodiment, the silicone polymer can be represented by the following structure (VI):

式中、Ａは、少なくとも１つの四級窒素基を含有し、ケイ素−炭素結合によってシリコーンブロックのケイ素原子に連結している基であり、各Ａは、独立して、同じであっても異なっていてもよく、Ｒ⁶は、約１〜約２２個の炭素原子のアルキル基、又はアリール基であり、各Ｒ⁶は、独立して、同じであっても異なっていてもよく、ｔは、０以上の値を有する整数であり、例えば、ｔは、２０未満又は１０未満であってよく、ｕは、約２００超、例えば、約２５０超、又は約３００超の整数であり、ｕは、約７００未満、又は約５００未満であってよい。ある実施形態によれば、Ｒ⁶は、メチルである。

Wherein A is a group containing at least one quaternary nitrogen group and connected to the silicon atom of the silicone block by a silicon-carbon bond, and each A is independently the same or different. R ⁶ is an alkyl group of about 1 to about 22 carbon atoms, or an aryl group, and each R ⁶ may independently be the same or different, and t is , An integer having a value greater than or equal to 0, for example, t may be less than 20 or less than 10, u is an integer greater than about 200, such as greater than about 250, or greater than about 300, and u is , Less than about 700, or less than about 500. According to certain embodiments, R ⁶ is methyl.

f. Grafted Silicone Copolyol The hair care composition of the present invention may comprise a grafted silicone copolyol in combination with a quaternized silicone polymer. This grafted silicone copolyol improves the spreadability of the quaternized silicone polymer by reducing the viscosity of the quaternized silicone polymer and can stabilize the quaternized silicone polymer in an aqueous conditioner matrix. It is considered possible. Further, by improving the spreadability as described above, it is considered that the hair care composition of the present invention can provide a better dry conditioning effect such as friction reduction and / or damage prevention as well as a reduction in stickiness. It has been. Surprisingly, the combination of a quaternized silicone polymer, a grafted silicone copolyol, and a cationic surfactant system comprising a dialkyl quaternized ammonium salt cationic surfactant compared to a similar combination. It was found that an improved friction reduction effect can be obtained. Such similar combinations include, for example, combinations in which the grafted silicone copolyol is replaced with an end-protected silicone copolyol, and the cationic surfactant system is a dialkyl quaternized ammonium salt cationic interface. Another combination is substantially free of active agent.

  The grafted silicone copolyol has a weight percent of grafted silicone copolyol to the mixture of grafted silicone copolyol and quaternized silicone copolymer of from about 1 wt% to about 50 wt%, alternatively from about 5 wt% to about 40 wt%. It is contained in the composition at a concentration such as by weight, or in the range of about 10% to 30% by weight.

  Grafted silicone copolyols useful herein are those having a silicone backbone, such as a dimethicone backbone, and a polyoxyalkylene substituent, such as a polyethylene oxide or / and polypropylene oxide substituent. The grafted silicone copolyols useful herein have a hydrophilic / lipophilic balance (HLB) value of from about 5 to about 17, such as from about 8 to about 17, or from about 8 to about 12. Grafted silicone copolyols having the same INCI name have varying weight ratios depending on the molecular weight of the silicone moiety and the number of polyethylene oxide or / and polypropylene oxide substituents.

  According to certain embodiments, exemplary commercially available grafted dimethicone copolyols, for example, have an HLB value of about 9 to about 12 and have the trade name Silsoft 430 available from GE (INCI name: “PEG / PPG-20 / 23 dimethicone”) having an HLB value of about 13 to about 17 and having the trade name Silsoft 475 (INCI name: “PEG-23 / PPG-6 dimethicone”), about 13 to Those having an HLB value of about 17 and having the trade name Silsoft 880 (INCI name: “PEG-12 dimethicone”), those having an HLB value of about 9 to about 12 and having the trade name Silsoft 440 (INCI name) : "PEG-20 / PPG-23 dimethicone"), having the trade name DC5330 available from Dow Corning (INCI name: “PEG-15 / PPG-15 dimethicone”).

  As described below, the quaternized silicone polymer and the grafted silicone copolyol are mixed and emulsified surfactant before being incorporated into the gel matrix formed by the cationic surfactant and the high melting point aliphatic compound. May be emulsified. This premix can improve the behavior of quaternized silicone polymers and grafted silicone copolyols, for example, increasing stability, decreasing viscosity, and more homogenous formulations with other components It is thought to form. Such emulsifying surfactants are about 0.001% to about 1.5%, alternatively about 0.005% to about 1.0%, or alternatively, based on the total weight of the hair conditioning composition It may be used at a concentration of about 0.01% to about 0.5% by weight. Such surfactants can be nonionic and can have an HLB value of about 2 to about 15, such as about 3 to about 14, or about 3 to about 10. Commercial examples of emulsifying surfactants include NIKKO Chemicals Co. , Ltd., Ltd. The non-ionic surfactant having an INCI name of C12 to C14 Pareth-3 having an HLB value of about 8 and supplied as a trade name NIKKOL T-3 is available.

  According to one embodiment, the hair care composition comprises a combination of two or more silicone conditioning agents along with an EDDS sequestering agent and a gel matrix.

In one embodiment, the hair care composition, (i) non-volatile, viscosity of the amino group a substantially free, and about 100,000 mm ² s ^-1 ~ about 30,000,000mm ² s ^-1 And (ii) a second non-volatile, substantially free of amino groups and having a viscosity of from about 5 mm ² s ⁻¹ to about 10,000 mm ² s ⁻¹ . A polyalkylsiloxane mixture comprising a polyalkylsiloxane, an aminosilicone having less than about 0.5% by weight nitrogen of the aminosilicone, and an internal phase greater than about 100 × 10 ⁶ mm ² s ⁻¹ when measured at 25 ° C. A silicone copolymer emulsion having a viscosity. For example, in another embodiment, the hair care composition is about 0.5% to about 10% by weight of (i) non-volatile, substantially free of amino groups, and about 100,000 mm ² s. first polyalkylsiloxane having a viscosity of ¹ to about 30,000,000mm ² s ^-1, and (ii) non-volatile, does not contain an amino group substantially, and about 5 mm ² s ^-1 to A polyalkylsiloxane mixture comprising a second polyalkylsiloxane having a viscosity of about 10,000 mm ² s ⁻¹ , and about 0.1 wt% to about 5 wt% of less than about 0.5 wt% of the aminosilicone An aminosilicone having nitrogen and about 0.1% to about 5% by weight of a silicone copolymer emulsion having an internal phase viscosity of greater than about 100 × 10 ⁶ mm ² s ⁻¹ when measured at 25 ° C. Including.

  In another embodiment, the hair care composition comprises a silicone polymer containing a quaternary group, the silicone polymer comprising a silicone block having greater than about 200 siloxane units, and a grafted silicone copolyol. For example, in another embodiment, the hair care composition comprises from about 0.1% to about 15% by weight of a silicone polymer containing quaternary groups having more than about 200 siloxane units. A grafted silicone copolyol at a concentration such that the grafted silicone copolyol in the mixture of the silicone polymer and the grafted silicone copolyol and the quaternized silicone polymer ranges from about 1% to about 50% by weight; ,including.

In yet another embodiment, the hair care composition has a viscosity of about 0.001 m ² / s to about 1 m ² / s (about 1,000 centistokes to about 1,000,000 centistokes), and amino An aminosilicone having less than about 0.5% by weight nitrogen of the silicone and (2) an internal phase viscosity greater than about 0.0001 × 1 m ² / s (about 120 × 10 ⁶ centistokes) when measured at 25 ° C. A silicone copolymer emulsion having:

2. Other Conditioning Agents The conditioning agents described by Procter & Gamble in US Pat. Nos. 5,674,478 and 5,750,122 are also suitable for use in the hair care compositions herein. is there. U.S. Pat. Nos. 4,529,586, 4,507,280, 4,663,158, 4,197,865, 4,217,914, The conditioning agents described in US Pat. Nos. 4,381,919 and 4,422,853 are also suitable for use herein.

a. Organic Conditioning Oil The hair care composition of the present invention may further comprise an organic conditioning oil. According to embodiments of the present invention, the hair care composition is combined with other conditioning agents such as silicone (described herein) from about 0.05% to about 3%, about 0.08%. % To about 1.5%, or even about 0.1% to about 1% by weight of at least one organic conditioning oil may be included as a conditioning agent. Suitable conditioning oils include hydrocarbon oils, polyolefins and fatty acid esters. Suitable hydrocarbon oils include hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated). Or unsaturated) (including but not limited to these polymers and mixtures). Linear hydrocarbon oils are typically about C12 to about C19. Branched chain hydrocarbon oils (including hydrocarbon polymers) typically contain more than 19 carbon atoms. Suitable polyolefins include liquid polyolefins, liquid poly-α-olefins, or even hydrogenated liquid poly-α-olefins. Polyolefins for use herein can be prepared by polymerization of C4 to about C14 or even C6 to about C12. Suitable fatty acid esters include, but are not limited to, fatty acid esters having at least 10 carbon atoms. These fatty acid esters include esters with hydrocarbyl chains derived from fatty acids or alcohols (eg, monoesters, polyhydric alcohol esters, and di- and tricarboxylic acid esters). The hydrocarbyl radical of the fatty acid ester may contain or be covalently linked to other compatible functional groups such as amide and alkoxy moieties (such as ethoxy or ether linkages).

3. Nonionic Polymer The hair care composition of the present invention may also further comprise a nonionic polymer. According to certain embodiments, the conditioning agent for use in the hair care composition of the present invention may comprise a polyalkylene glycol polymer. For example, polyalkylene glycols having a molecular weight greater than about 1000 are useful herein. Those having the following general formula (VIII) are useful.

式中、Ｒ¹¹は、Ｈ、メチル、及びこれらの混合物からなる群から選択され、ｖは、エトキシ単位の数である。ポリエチレングリコール等のポリアルキレングリコールは、本発明のヘアケア組成物に約０．００１重量％〜約１０重量％の濃度で含まれ得る。ある実施形態では、ポリエチレングリコールは、組成物の重量に基づいて最大約５重量％の量で存在する。本明細書で有用なポリエチレングリコールポリマーは、ＰＥＧ−２Ｍ（Ｐｏｌｙｏｘ ＷＳＲ（登録商標）Ｎ−１０としても知られており、Ｕｎｉｏｎ ＣａｒｂｉｄｅからＰＥＧ−２，０００として入手可能である）、ＰＥＧ−５Ｍ（Ｐｏｌｙｏｘ ＷＳＲ（登録商標）Ｎ−３５及びＰｏｌｙｏｘ ＷＳＲ（登録商標）Ｎ−８０としても知られており、Ｕｎｉｏｎ ＣａｒｂｉｄｅからＰＥＧ−５，０００及びポリエチレングリコール３００，０００として入手可能である）、ＰＥＧ−７Ｍ（ＰｏｌｙｏｘＷＳＲ（登録商標）Ｎ−７５０としても知られており、Ｕｎｉｏｎ Ｃａｒｂｉｄｅから入手可能である）、ＰＥＧ−９Ｍ（Ｐｏｌｙｏｘ ＷＳＲ（登録商標）Ｎ−３３３３としても知られており、Ｕｎｉｏｎ Ｃａｒｂｉｄｅから入手可能である）、及びＰＥＧ−１４Ｍ（Ｐｏｌｙｏｘ ＷＳＲ（登録商標）Ｎ−３０００としても知られており、Ｕｎｉｏｎ Ｃａｒｂｉｄｅから入手可能である）である。

Wherein R ¹¹ is selected from the group consisting of H, methyl, and mixtures thereof, and v is the number of ethoxy units. Polyalkylene glycols such as polyethylene glycol may be included in the hair care compositions of the present invention at a concentration of about 0.001% to about 10% by weight. In certain embodiments, the polyethylene glycol is present in an amount up to about 5% by weight based on the weight of the composition. The polyethylene glycol polymer useful herein is PEG-2M (also known as Polyox WSR® N-10 and available from Union Carbide as PEG-2,000), PEG-5M ( (Also known as Polyox WSR® N-35 and Polyox WSR® N-80, available from Union Carbide as PEG-5,000 and polyethylene glycol 300,000), PEG-7M (Also known as Polyox WSR® N-750, available from Union Carbide), PEG-9M (also known as Polyox WSR® N-3333, available from Union Carbide) In ), And PEG-14M is also known as (Polyox WSR (R) N-3000, a Union Carbide available from).

4). Suspending Agent The hair care composition of the present invention comprises a suspending agent in a concentration effective to suspend a water-insoluble substance in a form dispersed in the composition or to change the viscosity of the composition. Further, it may be included. Such concentrations range from about 0.1% to about 10%, or even from about 0.3% to about 5.0% by weight.

  Suspending agents useful herein include anionic polymers and nonionic polymers. As used herein, vinyl polymers such as crosslinked acrylic acid polymers having the CTFA name Carbomer, cellulose derivatives and modified cellulose polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, Crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seeds (Cydonia oblongamil Mill)), starch (rice, corn, jas) Potato, wheat), algal colloid (algae extract), microbiological polymer such as dextran, succinoglucan, pullulan, starch-based polymer such as carboxymethyl starch, methylhydroxypropyl starch, alginic acid-based polymer such as sodium alginate, alginic acid Propylene glycol esters, acrylate polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, polyethyleneimine, and inorganic water soluble materials such as bentonite, aluminum magnesium silicate, laponite, hectorite, and silicic anhydride are useful.

  Commercially available viscosity modifiers that are very useful herein are all B.I. F. Carbopol (R) 934, Carbopol (R) 940, Carbopol (R) 950, Carbopol (R) 980, and Carbopol (R) 981 carbomers, Rohm and Hass, available from the Goodrich Company ACRYSOL ™ 22 acrylate / steareth-20 methacrylate copolymer available from Amercell ™ POLYMER HM-1500 nonoxynyl hydroxyethyl cellulose, all available from Hercules Methyl cellulose with the name BENECEL (registered trademark), hydroxyethyl cellulose with the trade name NATROSOL (registered trademark), Hydroxylpropyl cellulose under the name KLUCEL®, cetyl hydroxyethyl cellulose under the trade name POLYSURF® 67, trade names CARBOWAX® PEG, POLYOX WASR, and UCON® fluid all supplied by Amerchol Examples include ethylene oxide and / or propylene oxide-based polymers.

  Other optional suspending agents include crystalline suspending agents that can be classified as acyl derivatives, long chain amine oxides, and mixtures thereof. These suspending agents are described in US Pat. No. 4,741,855.

  These suspending agents include, in one embodiment, ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms. In one embodiment, useful suspending agents include ethylene glycol stearate (both mono and distearate), but in one embodiment, distearate containing less than about 7% monostearate. . Other suitable suspending agents include alkanolamides of fatty acids having about 16 to about 22 carbon atoms, or even about 16 to 18 carbon atoms, examples of which include stearic acid mono Examples include ethanolamide, stearic acid diethanolamide, stearic acid monoisopropanolamide, and stearic acid monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (eg, stearyl stearate, cetyl palmitate, etc.), long chain esters of long chain alkanolamides (eg, stearamide diethanolamide distearate, stearamide mono). Ethanolamide stearate), and glyceryl esters (eg, glyceryl distearate, trihydroxystearin, tribehenine), commercially available examples are available from Rheox, Inc. Thixin® R, which is more available. In addition to the materials described above, long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanolamides of long chain carboxylic acids may be used as suspending agents.

  Other long chain acyl derivatives suitable for use as suspending agents include N, N-dihydrocarbylamide benzoic acid and its soluble salts (eg, Na, K), particularly N, N-di ( Hydrogenated) C16, C18 and tallow amide benzoic acid species, which are commercially available from Stepan Company (Northfield, Ill., USA).

  Examples of long chain amine oxides suitable for use as suspending agents include alkyl dimethyl amine oxides such as stearyl dimethyl amine oxide.

  Other suitable suspending agents include primary amines having fatty acid alkyl moieties having at least about 16 carbon atoms (examples include palmitamine or stearamine), and each containing at least about 12 carbon atoms. Secondary amines having two fatty acid alkyl moieties, such as dipalmitoylamine or di (hydrogenated tallow) amine. Still other suitable suspending agents include di (hydrogenated tallow) phthalamide and cross-linked maleic anhydride-methyl vinyl ether copolymer.

5. Adhesion aid The hair care composition of the present invention may further comprise an adhesion aid such as a cationic polymer. Cationic polymers useful herein are those having an average molecular weight of at least about 5,000, alternatively from about 10,000 to about 10,000,000, alternatively from about 100,000 to about 2,000,000. .

  Suitable cationic polymers include, for example, vinyl monomers having a cationic amine or quaternary ammonium functionality, acrylamide, methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, And copolymers with water-soluble spacer monomers such as vinylpyrrolidone. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol. Other suitable cationic polymers useful herein include, for example, cationic cellulose, cationic starch, and cationic guar gum.

  The cationic polymer may be included in the hair care composition of the present invention at a concentration of about 0.001% to about 10% by weight. In one embodiment, the cationic polymer is present in an amount up to about 5% by weight based on the weight of the composition.

Adhesion Polymer In a further embodiment of the invention, the composition of the invention may further comprise an adhesion polymer, preferably an anionic / acid adhesion polymer. The deposited polymer is at a concentration of about 0.03% to about 8%, preferably about 0.05% to about 3%, more preferably about 0.1% to about 1% by weight of the composition. included.

  The weight ratio of (i) the deposited polymer to the sum of (ii) monoalkylamine salt cationic surfactant, dialkyl quaternized ammonium salt cationic surfactant, and high melting point aliphatic compound is about 1: 1 to 1 It is preferred that it be about 1: 160, more preferably about 1: 2.5 to about 1: 120, even more preferably about 1: 3.5 to about 1:80. If the weight ratio of (i) to (ii) is too low, the composition may reduce adhesion of cationic surfactants, high melting point aliphatic compounds, and / or silicone compounds. If the weight ratio of (i) to (ii) is too high, the composition may affect the rheology and undesirably reduce the rheology of the composition.

Adhesion polymers useful herein include a vinyl monomer (A) having a carboxyl group in its structure and the following formula (1):
^{_{CH 2 = C (R 1)}} -CO-X- (Q-O) r -R 2 (1)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and Q is also substituted. Represents an alkylene group having 2 to 4 carbon atoms which may have a group, r represents an integer of 2 to 15, X represents an oxygen atom or an NH group, and has the following structure- (QO) _r— R ² , a vinyl monomer (B) represented by the number of atoms bonded to a straight chain is 70 or less),
Here, the vinyl monomer (A) is contained at a concentration of about 10% by mass to about 50% by mass, and the vinyl monomer (B) is contained at a concentration of about 50% by mass to about 90% by mass.

Vinyl monomer (A)
The copolymer of the present invention contains a vinyl monomer (A) having a carboxyl group in the structure. The copolymer may contain one vinyl monomer (A) or two or more vinyl monomers (A). The vinyl monomer (A) is preferably anionic.

  The vinyl monomer (A) is from about 10% by weight, preferably from about 15% by weight, based on the total weight of the copolymer, taking into account improved adhesion of cationic surfactants, aliphatic compounds, and / or silicones. , More preferably 20% by weight or more, even more preferably 25% by weight or more, and ˜about 50% by weight, preferably 45% by weight, taking into account that the smoothness does not deteriorate during application and / or the viscosity of the product Hereinafter, it is more preferably contained at a concentration of 40% by mass or less.

  Non-limiting examples of the vinyl monomer (A) having a carboxyl group include, for example, unsaturated carboxylic acid monomers having 3 to 22 carbon atoms. The unsaturated carboxylic acid monomer is preferably 4 or more carbon atoms, and preferably 20 or less carbon atoms, more preferably 18 or less carbon atoms, still more preferably 10 or less carbon atoms, even more preferably Has 6 or fewer carbon atoms. Furthermore, the number of carboxyl groups in the vinyl monomer (A) is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1.

In view of adhesion improvement of cationic surfactants, aliphatic compounds, and / or silicones, the vinyl monomer (A) is preferably an unsaturated carboxylic acid represented by the following formula (2) or formula (3): Acid monomers, more preferably those represented by formula (2).
^{_{CH 2 = C (R 3)}} -CO- (O- (CH 2) m -CO) n -OH (2)
(In the formula, R ³ represents a hydrogen atom or a methyl group, preferably a hydrogen atom, m represents an integer of 1 to 4, preferably 2 to 3, and n represents an integer of 0 to 4, preferably 0. ~ 2, most preferably 0.)
^{_{CH 2 = C (R 4)}} -COO- (CH 2) p -OOC- (CH 2) q -COOH (3)
(In the formula, R ⁴ represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and p and q independently represent an integer of 2 to 6, preferably 2 to 3).

  Examples of those represented by formula (2) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, angelic acid, tiglic acid, 2-carboxyethyl acrylate oligomer, and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable. Examples of those represented by formula (3) include acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, and the like.

Vinyl monomer (B)
The copolymer contains a vinyl monomer (B). The copolymer may contain one vinyl monomer (B) or two or more vinyl monomers (B). The vinyl monomer (B) is preferably nonionic.

  The vinyl monomer (B) is from about 50% by weight based on the total weight of the copolymer, considering the improvement in feel and smoothness during application, and of cationic surfactants, aliphatic compounds, and / or silicones. In consideration of adhesion improvement, it is contained at a concentration of about 90% by weight, preferably about 85% by weight, more preferably about 80% by weight, and even more preferably 75% by weight, based on the total weight of the copolymer. .

The vinyl monomer (B) useful herein has the formula (4):
^{_{CH 2 = C (R 1)}} -CO-X- (Q-O) r -R 2 (4)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and Q is also substituted. Represents an alkylene group having 2 to 4 carbon atoms which may have a group, r represents an integer of 2 to 15, X represents an oxygen atom or an NH group, and the structure — (Q—O) _r — In R ² , the number of atoms bonded to the straight chain is 70 or less.

When R ² has a substituent, the substituent is a substituent that does not react with the rest of the copolymer. The vinyl monomer (B) is preferably hydrophilic, and therefore R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or 1 or 2 An alkyl group having one carbon atom.

  X preferably represents an oxygen atom.

Q preferably represents an alkylene group having 2-3 carbon atoms which may also have a substituent, more preferably an alkylene group having 2-3 carbon atoms without a substituent. When the alkylene group of Q has a substituent, it is preferred that such substituents do not react with other portions of the copolymer, such substituents more preferably have a molecular weight of 50 or less, such as Even more preferably, such substituents have a molecular weight less than the structural portion of — (Q—O) _r —. Examples of such substituents include hydroxyl group, methoxy group, ethoxy group and the like.

  In consideration of improvement in adhesion of the cationic surfactant, aliphatic compound, and / or silicone, and / or smoothness during application, r is preferably 3 or more, and preferably 12 or less.

As described above, in the structure — (Q—O) _r —R ² , the number of atoms bonded by a straight chain is 70 or less. For example, when Q represents an n-butylene group, r = 15, and R ² represents an n-pentyl group, the number of atoms bonded to the straight chain of the structure — (Q—O) _r —R ² is , 80, which is out of the above range. The number of atoms bonded in a straight chain in the structure-(QO) _r -R ² improves adhesion of cationic surfactants, aliphatic compounds, and / or silicones, and / or smoothness during application. In consideration, it is preferably 60 or less, more preferably 40 or less, even more preferably 28 or less, and particularly preferably 20 or less.

  Examples of the vinyl monomer (B) include methoxypolyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (r in formula (4) is 2 to 15), polyethylene glycol (meth) acrylate (polyethylene glycol). The number of repetitions (r in formula (4) is 2 to 15), methoxypolyethylene glycol / propylene glycol (meth) acrylate (the number of repetitions of polyethylene glycol / propylene glycol (r in formula (4)) is 2 to 2. 15), polyethylene glycol / propylene glycol (meth) acrylate (repeating number of polyethylene glycol / propylene glycol (r in formula (4) is 2 to 15), methoxypolyethylene glycol / polybutyl Glycol (meth) acrylate (repeating number of polyethylene glycol / polybutylene glycol (r in formula (4) is 2 to 15), polyethylene glycol / polybutylene glycol (meth) acrylate (polyethylene glycol / polybutylene glycol) (R in formula (4) is 2 to 15), methoxypolyethylene glycol (meth) acrylamide (repeating number of polyethylene glycol (r in formula (4) is 2 to 15), And polyethylene glycol (meth) acrylamide (repeating number of polyethylene glycol (r in formula (4) is 2 to 15), preferably methoxy polyethylene glycol (meth) acrylate (of polyethylene glycol) Repetition number (r in formula (4) is 3 to 12), polyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (r in formula (4) is 3 to 12), methoxy Polyethylene glycol / propylene glycol (meth) acrylate (repeating number of polyethylene glycol / propylene glycol (r in formula (4) is 3 to 12), polyethylene glycol / propylene glycol (meth) acrylate (polyethylene glycol / propylene glycol) (R in formula (4) is 3 to 12), methoxypolyethylene glycol / polybutylene glycol (meth) acrylate (polyethylene glycol / polybutylene glycol repeat number (in formula (4)) r) is 3 to 12), polyethylene glycol / polybutylene glycol (meth) acrylate (repeating number of polyethylene glycol / polybutylene glycol (r in formula (4) is 3 to 12); More preferably, methoxy polyethylene glycol (meth) acrylate (the number of repetitions of polyethylene glycol (r in Formula (4) is 3 to 12)) and polyethylene glycol (meth) acrylate (the number of repetitions of polyethylene glycol (formula ( R) in 4) is 3-12).

Vinyl monomer (C)
In addition to the vinyl monomers (A) and (B), the copolymer provides a vinyl monomer having an alkyl group with 12 to 22 carbon atoms (C) in view of providing a conditioning effect such as smoothness during coating. ) May be further contained. When included, the amount of vinyl monomer (C) is based on the total weight of the copolymer, taking into account improved adhesion of cationic surfactants, aliphatic compounds, and / or silicones, and / or smoothness during application. Thus, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.

  Preferably, the vinyl monomer (C) is a (meth) acrylate monomer having an alkyl group having 12 to 22 carbon atoms in consideration of smoothness during coating. Furthermore, vinyl monomers having a branched alkyl group are particularly preferred.

  Examples of (meth) acrylate monomers having an alkyl group having 12 to 22 carbon atoms include myristyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cetyl ( (Meth) acrylate, lauryl (meth) acrylate, synthetic lauryl (meth) acrylate (but “synthetic lauryl (meth) acrylate” refers to alkyl groups having 12 carbon atoms and alkyl groups having 13 carbon atoms. The alkyl (meth) acrylate having). Among these, a (meth) acrylate monomer having an alkyl group having 12 to 20 carbon atoms is preferable, and a (meth) acrylate monomer having an alkyl group having 16 to 18 carbon atoms is more preferable.

  The copolymer may contain one vinyl monomer (C) or two or more vinyl monomers (C).

Other monomers In addition to the aforementioned vinyl monomers (A), (B), and (C), the copolymer may contain other vinyl monomers to the extent that the effect of the copolymer is not reduced. Examples of other vinyl monomers include, in addition to nonionic monomers, amphoteric monomers, semipolar monomers, cationic monomers, monomers containing polysiloxane groups, preferably having or having polysiloxane groups. There are no nonionic monomers. These other monomers are different from any of the aforementioned vinyl monomers (A), (B), and (C).

  Usually, the amount of such other monomers, if included, is 40% by weight or less of the total weight of the copolymer, preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight. It is as follows.

  In view of improved adhesion of cationic surfactants, aliphatic compounds, and / or silicones, the amount of cationic functional groups in the copolymer is preferably low, eg, cationic functional groups are preferably copolymer It occupies 10 mol% or less of all the functional groups therein. More preferably, the copolymer does not contain cationic functional groups.

  Examples of nonionic monomers include esters of (meth) acrylic acid and alcohols having 1 to 22 carbon atoms, amides of (meth) acrylic acid and alkylamines having 1 to 22 carbon atoms, Examples include monoesters of (meth) acrylic acid and ethylene glycol, 1,3-propylene glycol, and the like, esters in which the hydroxyl group of the monoester is etherified with methanol, ethanol, and the like, (meth) acryloyl monophorin, and the like .

  Examples of amphoteric monomers include (meth) acrylic esters having a betaine group, (meth) acrylamides having a betaine group, and the like.

  Examples of the semipolar monomer include (meth) acrylate having an amine oxide group, (meth) acrylamide having an amine oxide group, and the like.

  Examples of the cationic monomer include (meth) acrylate ester having a quaternary ammonium group, (meth) acrylamide having a quaternary ammonium group, and the like.

  A monomer containing a polysiloxane group is a monomer having a polysiloxane structure and a structure that can be covalently bonded to a copolymer. These component units typically have a high affinity for silicone oils used in combination in cosmetic material compositions and act by binding silicone oil to other component units in the copolymer to produce skin and It is believed to increase the adsorptive power of silicone oil to hair, particularly damaged hair.

The polysiloxane structure is a structure in which two or more repeating structural units represented by the following formula (4) are linked.
^{- (SiR 5 R 6 -O)} - (4)

In Formula (4), R ⁵ and R ⁶ independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group.

  The structure that can be linked to the copolymer via a covalent bond has a vinyl structure such as (meth) acrylate ester or (meth) acrylamide, and a structure that can be copolymerized with another monomer, a functional group such as thiol, and It may be a structure that can be linked to the copolymer by chain transfer during the polymerization, or a structure having an isocyanate group, a carboxylic acid group, a hydroxyl group, an amino group, etc., and capable of reacting and linking with a functional group on the copolymer. The structure is not limited.

  A plurality of these connectable structures can be present in a single monomer containing polysiloxane groups. In the copolymer, the polysiloxane structure can be connected to the main chain by a graft structure, or conversely, the polysiloxane structure can be a main chain that is connected to another structure by a graft structure. And other structures can be linked in a straight chain state by a block structure.

The monomer containing a polysiloxane group is preferably of the following formula (5):
^{_{CH 2 = C (R 7)}} -Z- (SiR 8 R 9 -O) s -R 10 (5)
(Wherein R ⁷ represents a hydrogen atom or a methyl group, R ⁸ and R ⁹ independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ¹⁰ represents 1 to Represents an alkyl group having 8 carbon atoms, Z represents a divalent linking group or a direct bond, and s represents an integer of 2 to 200).

  In view of the increased affinity for silicone oil, more preferably, s is 3 or more, even more preferably, s is 5 or more, and in consideration of enhanced copolymerization with other monomers, s is 50 or less.

Z represents a divalent linking group or a direct bond, but a linking group containing one or a combination of two or more of the structures suggested below is preferred. Although the number to combine is not specifically limited, Usually, it is 5 or less. Furthermore, the direction of the following structure is arbitrary (the polysiloxane group side may be any terminal). In the following, R represents an alkylene group or phenylene group having 1 to 6 carbon atoms.
-COO-R-
-CONH-R-
-O-R-
-R-

  Examples of the monomer represented by the above formula (5) include α- (vinylphenyl) polydimethylsiloxane, α- (vinylbenzyloxypropyl) polydimethylsiloxane, α- (vinylbenzyl) polymethylphenylsiloxane, α Examples include-(methacryloyloxypropyl) polydimethylsiloxane, α- (methacryloyloxypropyl) polymethylphenylsiloxane, α- (methacryloylaminopropyl) polydimethylsiloxane. One type of monomer containing a polysiloxane group may be used, or two or more types may be used in combination.

  In order to adjust the molecular weight and viscosity of the copolymer, a cross-linking agent such as a multifunctional acrylate may be introduced into the copolymer. However, in the present invention it is preferred that no crosslinker is included in the copolymer.

Structural analysis The amount of vinyl monomers (A), (B), and (C) in the copolymer, as well as other monomers, depends on the carbonyl group, amide bond, polysiloxane structure, various types of functional groups, carbon skeleton, etc. By using absorption or Raman scattering, various groups represented by ¹³ C-NMR, etc. in addition to ¹ H-NMR of methyl groups, amide bonding sites, and adjacent methyl and methylene groups in polydimethylsiloxane It can be measured by different types of NMR.

Weight average molecular weight The weight average molecular weight of the copolymer is preferably 3,000 or more, more preferably 5,000 or more, considering that it provides a conditioning effect by forming a complex with the cationic surfactant. , Even more preferably 10,000 or more, and considering the feel after drying, preferably about 2,000,000, more preferably 1,000,000 or less, even more preferably 500,000 or less, Even more preferably it is 100,000 or less, most preferably 50,000 or less.

  The weight average molecular weight of the copolymer can be measured by gel permeation chromatography (GPC). The developing solvent used in the gel permeation chromatography is not particularly limited as long as it is a commonly used solvent. For example, the measurement can be performed using a solvent blend of water / methanol / acetic acid / sodium acetate.

Viscosity The copolymer has a viscosity of 5 mPa · s or more and 50,000 mPa · s or less at 25 ° C. with respect to a 50% by mass aqueous carrier solution of a lower alkyl alcohol and a polyhydric alcohol, preferably an aqueous ethanol solution, more preferably an aqueous solution of butanediol. It is preferable to have. The viscosity is more preferably 10 mPa · s or more, and even more preferably 15 mPa · s or more, but more preferably 10,000 mPa · s or less, and even more preferably 5,000 mPa · s or less. The viscosity of the copolymer is preferably 5 mPa · s or more and 50,000 mPa · s or less from the viewpoint of handling. The viscosity can be measured using a BL type viscometer.

  Similar to the weight average molecular weight, the viscosity of the copolymer can be adjusted by controlling the degree of polymerization of the copolymer, and can be controlled by increasing or decreasing the amount of cross-linking agent such as multifunctional acrylate added.

6). Benefit Agent In certain embodiments, the hair care composition further comprises one or more additional benefit agents. Effective agents are from the group consisting of anti-dandruff agents, vitamins, fat-soluble vitamins, chelating agents, fragrances, brighteners, enzymes, sensation agents, attractants, antibacterial agents, dyes, pigments, bleaching agents, and mixtures thereof. Contains the selected material.

  In one aspect, the benefit agent may include an anti-dandruff agent. Such anti-dandruff particles must be physically and chemically compatible with the components of the composition and must not unduly compromise product stability, aesthetics, or performance.

  According to certain embodiments, the hair care composition comprises an anti-dandruff active substance, which may be anti-dandruff active substance particles. In certain embodiments, the anti-dandruff active is selected from the group consisting of pyridinethione salts; azoles such as ketoconazole, econazole and erviol; selenium sulfide; particulate sulfur; keratolytic agents such as salicylic acid; and mixtures thereof. In certain embodiments, the anti-dandruff particles are pyridinethione salts.

  Pyridinethione particles are a suitable particulate anti-dandruff active material. In one embodiment, the anti-dandruff active is a 1-hydroxy-2-pyridinethione salt and is in particulate form. In one embodiment, the concentration of pyridinethione antidandruff particles is from about 0.01% to about 5%, or from about 0.1% to about 3%, or from about 0.1% to about 2%. It is in the range of wt%. In one embodiment, the pyridinethione salt is zinc, tin, cadmium, magnesium, aluminum and zirconium, generally zinc, typically a zinc salt of 1-hydroxy-2-pyridinethione (“zinc pyridinethione” or “ZPT Are generally formed from heavy metals such as 1-hydroxy-2-pyridinethione salt in the form of platelet particles. In one embodiment, the platelet particle form of 1-hydroxy-2-pyridinethione salt has an average particle size of up to about 20 micrometers, or up to about 5 micrometers, or up to about 2.5 micrometers. Salts formed from other cations such as sodium may be suitable as well. Pyridinethione anti-dandruff actives include, for example, US Pat. No. 2,809,971, US Pat. No. 3,236,733, US Pat. No. 3,753,196, US Pat. No. 3,761,418, U.S. Pat. No. 4,345,080, U.S. Pat. No. 4,323,683, U.S. Pat. No. 4,379,753, and U.S. Pat. No. 4,470,982.

  In certain embodiments, the composition further comprises one or more antifungal and / or antibacterial actives in addition to the antidandruff active selected from polyvalent metal salts of pyrithione. In certain embodiments, the antibacterial active agent is coal tar, sulfur, charcoal, Whitfield ointment, castellani coating, aluminum chloride, gentian violet, octopirox (pyrocton olamine), cyclopirox olamine, undecylenic acid And its metal salts, potassium permanganate, selenium sulfide, sodium thiosulfate, propylene glycol, bitter orange oil, urea preparation, griseofulvin, 8-hydroxyquinoline siloquinol, thiobendazole, thiocarbamate, haloprozin, polyene, hydroxy Pyridone, morpholine, benzylamine, allylamine (terbinafine, etc.), tea tree oil, clove leaf oil, coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamic aldehyde, citronellic acid, HI Group consisting of chitol, ihithiol pail, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase, iodopropynylbutylcarbamate (IPBC), isothiazarinones such as octylisothiazinone, and azoles, and mixtures thereof Selected from. In certain embodiments, the antibacterial agent is selected from the group consisting of itraconazole, ketoconazole, selenium sulfide, coal tar, and mixtures thereof.

  In one embodiment, the azole antibacterial agent is benzimidazole, benzothiazole, bifonazole, butaconazole nitrate, crimbazole, clotrimazole, croconazole, evelconazole, econazole, erbiol, fenticonazole, fluconazole, flutimazole, isconazole, It is an imidazole selected from the group consisting of ketoconazole, lanoconazole, metronidazole, miconazole, neticonazole, omoconazole, oxyconazole nitrate, sertaconazole, sarconazole nitrate, thioconazole, thiazole, and mixtures thereof, or an azole antibacterial agent Is a triazole selected from the group consisting of terconazole, itraconazole, and mixtures thereof. The azole antibacterial active when present in the hair care composition is from about 0.01% to about 5%, or from about 0.1% to about 3%, or from about 0.3% to about It is included in an amount of 2% by weight. In certain embodiments, the azole antibacterial active is ketoconazole. In certain embodiments, the only antibacterial active is ketoconazole.

  Embodiments of the hair care composition may include a combination of antibacterial active substances. In one embodiment, the combination of antibacterial actives is octopirox and zinc pyrithione, pine tar and sulfur, salicylic acid and zinc pyrithione, salicylic acid and erviol, zinc pyrithione and erbiol, zinc pyrithione and crimbazole, octopirox and crimbazole, salicylic acid and octylol. Selected from the group of combinations consisting of Topirox and mixtures thereof.

  In certain embodiments, the composition comprises an effective amount of a zinc-containing layered material. In one embodiment, the composition is about 0.001% to about 10%, or about 0.01% to about 7%, or about 0.1% to about% by weight of the total weight of the composition. 5% by weight zinc-containing layered material.

  The zinc-containing layered material may be one in which crystal growth occurs mainly in two dimensions. It is customary that layer structures are not only those in which all atoms are incorporated in a distinct layer, but also have ions or molecules between the layers, called gallery ions (AF). Wells, “Structural Inorganic Chemistry”, Clarendon Press, 1975). Zinc-containing layered material (ZLM) can be incorporated into the layer and / or be a component of gallery ions. The following classes of ZLM represent relatively common examples in the general field and are not intended to be limiting with respect to a wider range of materials that meet this definition.

  Many ZLMs exist in nature as minerals. In some embodiments, the ZLM is selected from the group consisting of hydrozinc earth (zinc carbonate hydroxide), hydrozinc copper ore (zinc carbonate copper hydroxide), zinc peacock stone (copper zinc carbonate carbonate), and mixtures thereof. The Related minerals containing zinc may be included in the composition. There may also be natural ZLM in which anionic layer species such as clay minerals (eg phyllosilicates) contain ion exchanged zinc gallery ions. All of these natural substances may be obtained synthetically or formed in situ in the composition or in the manufacturing process.

Another common class of ZLM that is often, but not necessarily, synthetic is layered double hydroxides. In some embodiments, the ZLM is of the formula [M 2 ⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} A ^m− _{x / m} · nH ₂ O, where one of the divalent ions (M 2 ⁺ ). Part or all are zinc ions) (Crepaldi, EL, Pava, PC, Toronto, J, Valim, JB J. Colloid Interfac. Sci. Sci. 2002, 248, 429-42).

Still another type of ZLM, called hydroxy double salt, can be prepared (Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem. 1999, 38, 4211). 6). In one embodiment, the ZLM has the formula [M ²⁺ _1-x M ²⁺ _{1 + x} (OH) _{3 (1-y)} ] ⁺ A ⁿ⁻ _{(1 = 3y) / n} · nH ₂ O (formula Among them, the two metal ions (M ²⁺ ) may be the same or different) and are hydroxy double salts corresponding to each other. When the metal ions are the same and are represented by zinc, the formula is simplified to [Zn _{1 + x} (OH) ₂ ] ^{2x +} 2x A ⁻ .nH ₂ O. This latter formula represents materials such as zinc hydroxide chloride and zinc hydroxide nitrate (when x = 0.4). In one embodiment, the ZLM is hydroxy hydroxy chloride and / or hydroxy hydroxy nitrate. If divalent anions are replaced by monovalent anions, these are also related to hydrozincite. These materials may also be formed in situ in the composition or may be formed in a manufacturing process.

  In embodiments having a zinc-containing layered material and pyrithione or a polyvalent metal salt of pyrithione, the ratio of the zinc-containing layered material to the pyrithione or pyrithione polyvalent metal salt is about 5: 100 to about 10: 1, or about 2: 10 to about 5: 1, or about 1: 2 to about 3: 1.

The adhesion of the anti-dandruff active substance to the scalp is at least about 1 microgram / cm ² . Considering that the anti-dandruff active substance reaches the scalp and can be surely exerted there, the attachment of the anti-dandruff active substance to the scalp is important. In certain embodiments, the anti-dandruff active agent adheres to the scalp is at least about 1.5 microgram / cm ² , or at least about 2.5 microgram / cm ² , or at least about 3 microgram / cm ² , or At least about 4 microgram / cm ² , or at least about 6 microgram / cm ² , or at least about 7 microgram / cm ² , or at least about 8 microgram / cm ² , or at least about 8 microgram / cm ² , or At least about 10 micrograms / cm ² . Adhesion of the anti-dandruff active substance to the scalp is measured by a skilled beautician following a conventional cleaning protocol by washing an individual's hair with a composition containing the anti-dandruff active substance (eg, a composition according to the present invention). The The hair is then divided on the scalp area so that it can hold an open-ended glass cylinder on the surface, and at the same time, an aliquot of the extraction solution is added and stirred, and then the contents of the anti-dandruff active substance are recovered and conventional, such as HPLC Analytical quantification based on methodology.

Test Methods The test methods disclosed in the “Test Methods” section of this application are the same as the parameters of each of the Applicants ’inventions, as the Applicants’ inventions are described and claimed herein. It is understood that it should be used to determine the value.

A. Wet and Dry Conditioning Test Method This test method is designed to subjectively evaluate the basic performance of the rinse-off conditioner for both wet comb and dry comb. In a typical test, 3-5 separate formulations can be evaluated for their performance. The assessment may include a control treatment that does not contain silicone and contains a high concentration of silicone to facilitate performance differentiation. The substrate is uniform, untreated brown hair that can be obtained from various sources screened to ensure that there is no noticeable surface damage or less lift of decolorized damaged hair. is there.

B. Treatment Procedure: 4 to 5 4 grams long 20.3 cm (8 inch) switches are assembled in a hairpiece holder and medium hard water (0.05 to 0.17 g / L for 10 seconds at 39 ± 1 ° C.) ) (3-10 gpg) to wet to ensure complete wetting. Drain the tress lightly, and over the entire length of the tress, from the bottom of the holder 2.5 cm (1 inch) to the tip, a concentration of 0.1 g product per gram of dry hair (0.1 g / 1 g Apply a washing shampoo uniformly with 2 g) of hair or 20 g of hair. A bundle of switch combo is foamed for 30 seconds by friction, which is a typical operation used by consumers, and an additional 30 with 39 ± 1 ° C water flowing at 5.68 L / min (1.5 gal / min). Rinse for a second (while moving the hair by hand) to ensure complete rinsing. This process is repeated. Conditioner treatment is applied in the same way as the shampoo (reducing to 0.1 g / 1 g hair, or 0.05 g / 1 g hair in the case of a more concentrated prototype) and spread over the entire bunched for 30 seconds. Leave for an additional 30 seconds and rinse thoroughly with an additional 30 seconds of hand movement. The tufts are drained lightly, separated from each other, hung on a rack so that the tufts do not come into contact with each other, and loosened with a coarse comb.

C. Scoring Procedure To assess wet combs using a trained scorer, bunches are separated into five on the rack and one tress from each treatment is included in the rating set. Only two comb evaluations are performed for each tuft. The scorer is asked to compare treatments by comb street, but using a fine nylon comb that is typical for consumers, it is easy on a 0 to 10 basis. / Evaluate the difficulty. Ten separate evaluations are collected and the results are analyzed by a statistical analysis package to verify statistical significance. Statistical significance of differences between treatments is determined using Statgraphics Plus 5.1.

  The comb is transferred to a temperature and humidity controlled room (22 ° C./50% RH) and dried overnight for comb-like evaluation in the dry state. They remain separated, as described above, and the panelists will evaluate the ease of combing in the center of the tuft in the dry state, the ease of combing at the tip in the dry state, and tactile evaluation of the tip feel. By performing these three evaluations, it is required to evaluate the dry conditioning performance. The same ten criteria are used for these comparisons. Again, each panel set is evaluated by only two panelists. Statistical analysis to separate the differences is performed using the same method as described above.

D. Friction reduction (IFM) in dry hair
In addition, dry conditioning performance is evaluated by measuring the hair friction force using an Instron test apparatus (Instron 5542, Instron, Inc .; Canton, Mass., USA). In a typical procedure, hair tresses are first prepared according to treatment protocol C and dried overnight in a temperature and humidity controlled (22 ° C./50% RH) room. The frictional force (grams) between the hair surface and the urethane pad is measured along the hair and measured three times per tress.

  The following examples illustrate the invention. The compositions listed in the examples can be prepared by conventional formulation and mixing techniques. It will be understood that other modifications of the present invention within the skill of the specialist in the field of hair care formulations may be made without departing from the spirit and scope of the present invention. All parts, percentages, and ratios herein are by weight unless otherwise specified. Some components may be obtained as a dilute solution from suppliers. The amounts stated represent the percentage by weight of the active substance, unless otherwise specified.

  The following are non-limiting examples of hair care compositions included in embodiments of the present invention.

Rinse-off conditioners Examples 1-16
In Table 1, the deposition aid polymer is an anionic deposition polymer. Examples 1 to 12, 14 and 16 are reference examples.

¹ ベヘニルトリメチルアンモニウムメチルスルフェート（Ｆｅｉｘｉａｎｇ製）
² ベヘニルトリメチルアンモニウムクロリド、Ｇｅｎａｍｉｎ ＫＤＭＰ（Ｃｌａｒｉａｎｔ製）
³ ＨＹ−３０５０（Ｄｏｗ Ｃｏｒｎｉｎｇ製）
⁴ ＨＹ−３０５１（Ｄｏｗ Ｃｏｒｎｉｎｇ製）
⁵ Ｙ−１４９４５；１０，０００ｃｐｓアミノジメチコン（Ｍｏｍｅｎｔｉｖｅ製）
⁶ ＡＢＣ１４５９（Ｍｉｔｓｕｂｉｓｈｉ Ｃｈｅｍｉｃａｌ製）

¹ behenyltrimethylammonium methyl sulfate (manufactured by Feixiang)
² behenyl trimethyl ammonium chloride, Genamin KDMP (manufactured by Clariant)
³ HY-3050 (manufactured by Dow Corning)
⁴ HY-3051 (manufactured by Dow Corning)
⁵ Y-14945; 10,000 cps amino dimethicone (manufactured by Momentive)
⁶ ABC1459 (manufactured by Mitsubishi Chemical)

  Comparative example

  Wet and dry conditioning tests

  FIG. 1 is a graph showing a comparison of HY-3050 and HY-3050 + adhered polymer by measuring units of frictional force (grams). FIG. 2 is a graph showing a comparison of HY-3051 and HY-3051 + deposited polymer by measuring units of frictional force (grams). FIG. 3 is a graph showing a comparison between HY-3050 and HY-3050 + adherent polymer, where dry conditioning performance is evaluated by hair friction force measurement (IFM index). FIG. 4 is a graph showing a comparison between HY-3051 and HY-3051 + adhered polymer, where dry conditioning performance is evaluated by hair friction force measurement (IFM index).

  These results show that the deposited polymer significantly reduces dry hair friction (measurement error ± 0.05) compared to a similar formulation without the deposited polymer.

  In one embodiment of the present invention, the oligomer obtained from the metathesis of unsaturated polyol ester may have a melting point in the range of 30-100 ° C, but in a further embodiment, the melting point was about 40-90 ° C. It's okay. Without being bound by theory, the present invention may use higher melting points, such as greater than 30 ° C., for example in terms of elasticity of such metathesically unsaturated polyol esters in combination with attached polymers, such as processing and For handling, it has been found that such metathesis unsaturated polyol esters may have a melting point of less than 100 ° C.

  The hair care compositions of the present invention may be present in typical hair care formulations. The composition may be in the form of a solution, dispersion, emulsion, powder, talc, capsule sphere, sponger, solid dosage form, foam, and other delivery mechanism. Compositions of embodiments of the present invention are in hair tonics, leave on hair products (eg, treatment and styling products), rinse off hair products (eg, shampoos and conditioners), and any other form that can be applied to hair. It's okay.

  According to one embodiment, the hair care composition is a porous dissolvable solid structure, such as US Patent Application Publication Nos. 2009/0232873 and 2010/0179083, which are hereby incorporated by reference in their entirety. It may be provided in a form such as that provided.

  Hair care compositions are generally prepared by conventional methods such as those known in the art of making compositions. Such methods typically involve mixing the ingredients in one or more steps with or without heating, cooling, application of vacuum, etc. to a relatively uniform state. The composition is prepared to optimize stability (physical stability, chemical stability, light stability) and / or delivery of the active agent. The hair care composition may be present in a single phase or single product, or the hair care composition may be present in a separate phase or separate product. If two products are used, they may be used together or sequentially. Sequential use may occur in a short time, such as immediately after use of a single product, or may occur over a period of hours or days.

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 millimeters” is intended to mean “about 40 millimeters”.

  All references cited herein, including any cross-references or related patents or related applications, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. Citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, or is alone or in any other reference ( No admission is made to teach, suggest or disclose such invention in any combination with the singular or plural number. Further, in this document, the meaning assigned to a term in this document if the scope of any meaning or definition of the term contradicts any meaning or definition of a similar term in a document incorporated by reference. Or it shall conform to the definition.

  While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (17)

A hair care composition comprising:
a. 0.05% to 15% by weight of the hair care composition of one or more metathesically unsaturated polyol ester oligomers;
b.
i. From 0.1% to 20% by weight of the hair care composition of one or more high melting point aliphatic compounds;
ii. 0.1 wt% to 10 wt% cationic surfactant system of the hair care composition, and iii. A gel matrix comprising at least 20% by weight of an aqueous carrier of the hair care composition;
c. 0.03% by weight to 8% by weight of an anionic adhesion polymer, wherein the anionic adhesion polymer has 10% by mass to 50% by mass of a vinyl monomer (A) having a carboxyl group in the structure, and the following formula ( 1):
^{_{CH 2 = C (R 1)}} -CO-X- (Q-O) r -R 2 (1)
(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and Q represents a substituent. Represents an alkylene group having 2 to 4 carbon atoms, r represents an integer of 2 to 15, X represents an oxygen atom or an NH group, and has the following structure-(QO) _r- R ² is a copolymer containing, as a monomer unit, a vinyl monomer (B) represented by 50 to 90% by mass represented by the following formula: A) is the formula (2):
^{_{CH 2 = C (R 3)}} -CO- (O- (CH 2) m -CO) n -OH (2)
(Wherein R ³ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4, and n represents an integer of 0 to 4), and an anionic adhesion polymer. Composition.   The hair care composition of claim 1 comprising 0.1% to 10% by weight of the one or more oligomers of the hair care composition.   The hair care composition according to claim 1 or 2, comprising 0.25% to 5% by weight of the one or more oligomers of the hair care composition.   The hair care composition according to any one of claims 1 to 3, wherein the one or more oligomers are triglyceride oligomers.   The hair care composition according to any one of claims 1 to 4, wherein the one or more oligomers are soybean oligomers.   The hair care composition according to any one of claims 1 to 5, wherein the soybean oligomer is completely hydrogenated.   The hair care composition according to any one of claims 1 to 5, wherein the soybean oligomer is hydrogenated by 80% or more.   8. A hair care composition according to any one of the preceding claims, wherein the hair care composition further comprises one or more further conditioning agents.   9. A hair care composition according to claim 8, wherein the further conditioning agent is silicone.   The hair care composition comprises 1: 1 to 1: 160 (i) the anionic adhesion polymer; (ii) a monoalkylamine salt cationic surfactant, a dialkyl quaternized ammonium salt cationic surfactant; The hair care composition as described in any one of Claims 1-9 containing the weight ratio with the sum total of a high melting point aliphatic compound.   The hair care composition according to any one of claims 1 to 10, wherein the hair care composition comprises the anionic adhesion polymer that is a copolymer having a weight average molecular weight of 3,000 to 50,000.   The hair care composition according to any one of claims 1 to 11, wherein the hair care composition comprises one or more metathesized unsaturated polyol ester oligomers having a melting point in the range of 30 to 100 ° C. The hair care composition is
a. One or more metathesized unsaturated polyol ester oligomers having a melting point in the range of 30-100 ° C.,
b. The hair care composition according to any one of claims 1 to 12, wherein the ratio of the one or more oligomers to the anionic adhesion polymer is 0.40 to 5.0.   The hair care composition according to any one of the preceding claims, wherein the hair care composition further comprises one or more further benefit agents. 15. Hair care according to claim 14, wherein the further benefit agent is selected from the group consisting of antidandruff agents, vitamins, chelating agents, fragrances , enzymes , antibacterial agents, dyes, pigments, bleaching agents, and mixtures thereof. Composition.   The hair care composition according to any one of the preceding claims, wherein the one or more oligomers are self-metathesized.   The hair care composition according to any one of claims 1 to 16, wherein the one or more oligomers are cross-metathesized.

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